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Article

The Evaluation and Analysis of the Anti-Corrosion Performance of the Sealing Material B72 for Metal Artifacts Based on Electrochemical Noise

by
Hao Xu
1,
Minghao Jia
2,
Pei Hu
3,4,
Shengyu Liu
1,5,* and
Gang Hu
1,6,*
1
School of Archaeology and Museology, Peking University, Beijing 100871, China
2
Institute of Archaeology, Chinese Academy of Social Sciences, Beijing 100710, China
3
Beijing Advanced Innovation Center for Soft Matter Science and Engineering, Beijing University of Chemical Technology, Beijing 100029, China
4
Key Scientific Research Base of Scientific & Technological Evaluation (Beijing University of Chemical Technology), National Cultural Heritage Administration, Beijing 100029, China
5
Key Laboratory of Archaeomaterials and Conservation, Ministry of Education, Institute for Cultural Heritage and History of Science & Technology, University of Science and Technology Beijing, Beijing 100083, China
6
Key Laboratory of Archaeological Science, Ministry of Education, School of Archaeology and Museology, Peking University, Beijing 100871, China
*
Authors to whom correspondence should be addressed.
Coatings 2024, 14(9), 1190; https://doi.org/10.3390/coatings14091190
Submission received: 17 August 2024 / Revised: 9 September 2024 / Accepted: 13 September 2024 / Published: 14 September 2024
(This article belongs to the Special Issue New Trends in Conservation and Restoration of Cultural Heritage)
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Abstract

:
Paraloid B-72 (B72), as a transparent, colorless polymer material, has good film-forming ability when dissolved in acetone and is widely used as a sealing material for metal artifacts. In order to analyze and evaluate the preservation performance of B72 as a sealing material on the substrate of metal artifacts, a variety of electrochemical methods, mainly electrochemical noise (EN), and scanning electron microscopy (SEM) were applied to evaluate the B72 coating. The results showed that the B72 coating had a good preservation effect at the initial stage, and its poor water resistance led to the loss of its effectiveness after a few days of immersion. Compared with conventional electrochemical methods, electrochemical noise is non-destructive, which cannot cause new corrosion on the metal substrate and can well characterize the corrosion rate of the test system, and the results of its time domain and frequency domain analyses can correspond well with the polarization resistance and impedance spectra. Electrochemical noise is an effective method for evaluating the anti-corrosion performance of material preservation coatings.

1. Introduction

Electrochemical noise (EN) is the phenomenon of random non-equilibrium fluctuations in the electrical state parameters of an electrochemical kinetic system during its evolution, which are caused by irreversible reactions at the electrode–electrolyte interface. Compared with conventional electrochemical methods, electrochemical noise has the advantages of being non-destructive in situ and has a short measurement time without any requirement for stability. Therefore, this method can be widely used in the practice of corrosion monitoring [1,2].
Since the 1960s, when Iverson [3] discovered transient fluctuations of voltage on corroded metals, scholars have begun to systematically study electrochemical noise. Initially, EN was carried out under constant potential or constant current to study the noise of current or potential separately [4,5]. In the 1980s, under the research of Eden and Hladky [6,7,8,9,10], the disturbance-free, dual-working electrode measurement in the ZRA mode was proposed, which made it possible to detect fluctuations of current and potential at the same time and to have a better cognition of metal corrosion. In addition to the improvement in the measurement method, different measurement parameters such as noise resistance Rn [11,12,13], noise impedance Zn [14,15,16,17], localized corrosion parameter LI [18,19], as well as the frequency of events (fn) and the average charge in each event charge (q) in shot noise theory [1,20,21,22] have been proposed thanks to the efforts of previous researchers. Different data processing methods such as Fourier Transform (FFT) [23], Discrete Wavelet Transform (DWT) [24,25,26], Empirical Mode Decomposition (EMD) [27], and Hilbert–Huang Transform (HHT) [28,29] have been applied in practice to assist in the differentiation of signals. EN has been developed and applied to several fields of corrosion detection, including corrosion pattern recognition [21,30], corrosion behavior study [31,32], and anti-corrosion coating evaluation [33,34,35,36,37].
In the field of metal artifact preservation, electrochemical corrosion is dominant in metal corrosion [38], so the use of electrochemical methods to study the corrosion behavior of metals is very important for their preservation. At present, conventional electrochemical methods such as polarization curves and electrochemical impedance spectroscopy have been maturely applied to the selection and evaluation of corrosion inhibitors and sealing materials for metal artifacts [39,40,41] while EN is seldom used. But in industry, EN is also commonly used for the evaluation of organic coatings. A detailed review study was carried out by Jing et al. [42]. Skerry and Eden used potential noise and current noise to evaluate the protective performance of coatings. Mills and Mabbutt [43] used noise resistance (Rn) to quantitatively evaluate the protective performance of coatings, which is widely used today. Mills [44] and Jamali [33] et al. improved the apparatus for EN, such as NOSC and SC, to make EN more suitable for in situ measurement. Moreover, the conventional electrochemical methods can cause some corrosion to the test site, which is contrary to the principle of cultural relic preservation [38], while EN, with its non-destructive, in situ, easy-to-measure characteristics, among others, coincides with the above principle.
Paraloid B-72 (B72), commonly used as a sealing material in metal artifact preservation [38,45,46], is also used for other applications, such as adhesives in the process of bonding, filling, and coating—painting of ceramics [47,48], emergency preservation of excavated ivory [49], and the reinforcement of painted pigments [50]. B72 has been mostly studied by scholars for its light aging resistance [51,52], while less electrochemical evaluations have been conducted. The aim of this work is to conduct electrochemical noise measurements on B72, to assist other conventional electrochemical methods for validation, to investigate its electrochemical corrosion behavior, and to explore the feasibility of EN in the evaluation of sealing materials for metal artifacts.

2. Materials and Methods

2.1. Materials

The test samples were made of A3 carbon steel, which contained 0.18% C, 0.25% Si, 0.50% Mn, 0.022% S, and 0.018% P (mass ratio). The samples were rectangular plates of 25 × 50 mm dimensions and thickness of 3 mm. Rust-free and polished A3 carbon steel was prepared in the phosphoric acid alcohol solution (5% phosphoric acid + 10% anhydrous ethanol) as well as the ultrasonic removal of the oil film attached to the surface of the carbon steel. Then, we used 600-, 1000-, and 3000-grit sandpaper in order to sand and then polish. After polishing, we used anhydrous ethanol to wipe the surface.
The samples were divided into two groups, the blank group and the B72 group, with two samples for each group. The blank group was not treated, and the coating of the B72 group was referred to the heritage conservation practice [38,46] by preparing a 2% concentration of B72 (The Daw Chemical Company, Maitland, MI, USA) acetone solution and brushing it onto the A3 carbon steel. In this article, different ways of coating the B72 film were also experimented with, with brushing on the left and immersion on the right, as shown in Figure 1. The result showed that brushing can make the film uniform and transparent.

2.2. Methods

The methods are based on electrochemical measurements, combined with morphological observation of the sample surface. All electrochemical measurements were carried out employing the CS-350 (CorrTestTM, Wuhan, China). The electrolyte solution was 3.5 wt% NaCl solution. The reference electrode was a saturated Ag/AgCl electrode, and the counter electrode was a platinum mesh electrode. The test area is controlled at about 1 cm2 in all measurements.
Electrochemical noise measurements (ENMs) were carried out in the ZRA mode using the salt bridge (SB) arrangement [44,53,54], as shown in Figure 2a, with a sampling duration of 30 min and a sampling frequency of 10 Hz. EIS measurements were executed at open circuit potential (OCP) within the frequency domain 10 kHz to 0.01 Hz using a sine wave of 10 mV amplitude peak to peak. Polarization curves were provided at a scan rate of 0.5 mV·s−1 from −100 mV to +100 mV of OCP. The arrangement for EIS and Polarization curve measurements is shown in Figure 2b.
The morphology of the sample surface was observed using a scanning electron microscope (Thermo Fisher Scientific Quattro ESEM, Waltham, MA, USA) with EDS (Thermo Fisher Scientific Quattro ESEM EDS, Waltham, MA, USA) at an accelerating voltage of 10–15 kV, a beam current of 3.5–4.0, and the imaging option of a secondary electron image. For organic coating, the sample surface was sprayed with gold to enhance electrical conductivity.

3. Results and Discussion

3.1. Time Domain Analysis and Polarization Resistance

The time domain analysis focused on obtaining the three statistical parameters of voltage standard deviation (σV), current standard deviation (σI), and noise resistance (Rn). The DC drift trend was removed using Matlab self-programming code. The removal of the DC trend is important for data analysis of EN both in time and frequency domains. The DC trend is often considered to be caused by some unavoidable nonstationary condition during the measurement process, which leads to slow changes in the measured parameters (e.g., potential and current). When DC trends are considered, we expect that the precision of its statistical parameters will deteriorate [55].
The STDEV.P function in Excel was used to calculate the σV and the σI. The noise resistance can be calculated according to Equation (1) [11]. The time domain data after de-trend were shown in Figure 3 and Figure 4.
Rn = σV/σI,
Rn is considered to be equivalent to the polarization resistance (Rp) [11]. The polarization curves at different immersion times are shown in Figure 5. With the extension of immersion time, the blank group showed an increase in the self-corrosion potential and a stable self-corrosion current, while the B72 group showed a significant decrease in the self-corrosion potential and an increase in the self-corrosion current. Since EN had two working electrodes, two measurements were taken. Taking “A3-1-1D” as an example, “-1” represented WE1, and “-1D” represented the first day of immersion (immersed for 24 h). The impedance spectra were measured in the same way.
The weakly polarized region (±0.02 V) of the polarization curves was fitted using C-view 2.0 software, and the average value of the polarization resistances of the two working electrodes was taken as Rp and compared with Rn, as shown in Figure 6 and Figure 7 below.
The standard deviation of current and potential is a statistical measure of the fluctuation of current and potential, the degree of fluctuation which in turn reflects the corrosion rate. Previous studies [53,56] have shown that highly protective coatings have larger σV as well as smaller σI, while the opposite is true for low protective coatings. Good protection limits the penetration of electrolytes, which in turn attenuates the current and the attenuation of the current leads to potential instability.
The blank group corresponded to Figure 6. σV and σI gradually decreased and stabilized after 1d. σV decreased from 7 × 10−5 V to 2 × 10−5 V, and σI decreased from 4 × 10−8 A to 5 × 10−9 A (Figure 6a), which indicated that in the early stage, the fluctuations of potential and current were greater, and the corrosion rate was larger. But after 1 d, the potential and current fluctuations decreased, and the overall stabilization state was reached, which corresponded to the gradual increase of Rn from 2 kΩ to 4 kΩ (Figure 6b).
The B72 group corresponds to Figure 7. σV decreased while σI increased, and then both were stabilized after 2 d. σV decreased from 2 × 10−5 V to 1 × 10−5 V and then was stabilized, and σI increased from 5 × 10−10 A to 4 × 10−9 A with a slight tendency to increase, which was consistent with the description of the degradation of the coating’s protective properties as mentioned above. Compared with different stages, in the early stage, there is a high level of σV and a low level of σI, but after 2 d, there is a low level of σV and a high level of σI, which indicates that the protective property of the coating decreases, and the corresponding Rn gradually decreases from 40 kΩ to about 5 kΩ and then remains stable.
In terms of the comparison between Rp and Rn, they could not match exactly numerically but remained consistent in the overall trend. Both Rn and Rp in the blank group increased slowly with the increase in immersion time, while in the B72 group, they decreased gradually and remained stable after 2 d.
In this test, the Rn has the ability to characterize the change in the Rp, and EN is able to obtain corrosion parameters with the same evaluation ability without applying DC polarization, which conservators do not want to use on the artifacts.

3.2. Frequency Domain Analysis and Impedance Spectra

Data processing in the frequency domain was carried out with the European Cooperative Group on Corrosion Monitoring of Nuclear Materials (ECG-COMON) software (available for free on https://ecg-comon.org/) [57,58,59]. The PSDs were calculated by dividing each raw data ASCII file into 17 sections of 2048 data points to obtain averaged PSDs by using the fast Fourier transform (FFT) method after having linearly de-trended each section and applying Hann window on the de-trended section.
The current and potential PSDs as well as noise impedance Zn at different immersion times are shown in Figure 8 and Figure 9. The Zn can be calculated according to Equation (2) [60].
Zn(f) = [ΨV(f)/ΨI(f)]1/2,
The purpose of the power spectral density (PSD) is to describe the magnitude of the signal power at different frequencies. This allows us to assess the corrosion rate from the PSD of current. Previous studies also showed that signals in the low-frequency band (0.1–1 Hz) correspond to most corrosion events, from which corrosion patterns can be recognized [61,62,63].
Figure 10 shows the comparison of the current PSD and noise impedance Zn of the two groups at different immersion times (0 d and 6 d). In Figure 10a (for current PSD), at the beginning of immersion (0 d), the power density of the blank group was larger than that of the B72 group in the measured frequency range. Taking the low frequency (0.01 Hz) as an example, 5 × 10−12 A2·Hz−1 (blank group) was greater than 5 × 10−16 A2·Hz−1 (B72 group), a 1000 times difference in power density. Therefore, it can be seen that the corrosion rate of the B72 group was less than that of the blank group at the beginning of immersion.
At the late stage of immersion (6 d), the corrosion stabilization in the blank group resulted in a decrease in power density from 5 × 10−12 A2·Hz−1 to 1 × 10−14 A2·Hz−1 (at 0.01 Hz), which in turn indicated a decrease in the corrosion rate. In contrast, due to the breakdown of the protective coating, the B72 group had an increase in power density from 5 × 10−16 A2·Hz−1 to 1 × 10−14 A2·Hz−1 (at 0.01 Hz), which was similar to that of the blank group.
Previous studies [14,57,64] have shown that the noise impedance (Zn) has the same magnitude as the impedance modulus and can measure the corrosion rate. Therefore, this article also focused on the magnitude of Zn at the low frequency (0.01 Hz). In Figure 10b, at the early stage (0 d), the B72 group had a resistance of about 50 kΩ at 0.01 Hz, while the blank group had only 4 kΩ, but after a long period of immersion (6 d), the Zn (at 0.01 Hz) of the B72 group decreased to 3 kΩ, which was slightly higher than that of the blank group of 2 kΩ, indicating that the B72 coating had almost lost its protective ability.
Figure 11 and Figure 12 show the results of electrochemical impedance spectra (EIS). The data were processed using the Z-view 2.0 software from Corrtest.
In Figure 11a, the impedance modulus of the blank group fluctuates between 2 and 3 kΩ and was relatively stable with a slight decrease. In Figure 11b, the frequency corresponding to the time constant decreased from 10 Hz to 0.2 Hz (the peak was shifted to the right), indicating that the rust was more difficult to polarize in comparison with the original pure iron surface. The phase angle in the high frequency (105 Hz) region did not change, indicating that the newly generated rust did not form a film.
In Figure 12a, the impedance modulus of the B72 group varied considerably, decreasing from 100 kΩ (0 d) to 4 kΩ (6 d). In Figure 12b, two time constants (two peaks) showed that B72 had good film formation on the surface of the carbon steel, but after 5 d, there was only one time constant, which indicated that the B72 film had lost its effect, and the phase plot of the B72 group was similar to that of the blank group.
Figure 13 shows together the impedance modulus and noise impedance for the blank group and the B72 group. For the two groups, the impedance modulus and Zn had a good overlap in the low-frequency stage (<1 Hz). This shows that ENM can simply and quickly accomplish the measurement of the impedance modulus without applying any disturbance and then reflect the corrosion rate.

3.3. Scanning Electron Microscope

Figure 14 shows that before immersion, the sample had a few defects of its own (Figure 14a). The B72 coating had almost no ripples on the sample surface (Figure 14b), indicating that the acetone solution of B72 had good fluidity and formed a uniform film on the sample surface.
In Figure 15a, during the long immersion process, loose and porous rust was generated on the surface of the blank group. In Figure 15b, there was a pitting hole in the B72 film. New rust in this hole had broken the film. In Figure 15c, the film was wrinkled, indicating that the B72 film had lost its bond with the substrate after immersion.
Elemental analyses of the “white” material on the surface of the coating were performed (like Figure 15b), and the result is shown in Figure 16. The EDS result showed that the material was rich in Fe and O, which should be the new iron rust. It indicated that corrosion occurred on the surface of the film even though there were no pitting or cracks.

4. Conclusions

In this paper, the following conclusions were obtained via the above experiments:
  • The comparison between the time and frequency domain analysis of electrochemical noise and the conventional electrochemical methods had good consistency, which indicated that the ENM can well characterize the corrosion rate of the measured system. The electrochemical noise technique can non-destructively obtain parameters similar to the polarization resistance Rp and impedance modulus compared with conventional electrochemical methods. The electrochemical noise technique required less stability than the polarization curves and electrochemical impedance spectroscopy technique, which was more suitable for on-site measurements.
  • In the time domain analysis, the σI showed a gradual decrease in the corrosion rate in the blank group and a gradual increase in the corrosion rate in the B72 group, which was consistent with the macroscopic recognition of corrosion. Meanwhile, the noise resistance Rn and polarization resistance Rp showed consistency in trend although they were not exactly the same in value.
  • In the frequency domain analysis, the current PSD can reflect the distribution of the power of the current density at different frequencies, which in turn reflects the corrosion rate of the system. Furthermore, the noise impedance in the low-frequency band and the impedance modulus can match well.
  • Regarding the B72 sealing material itself, the sealing coating had a good protective effect on the metal artifacts in the initial stage. Both Rp and impedance modulus or Rn and Zn were higher than that of the blank group, which indicated that B72 had a good inhibition of corrosion but almost lost its effect after a short period (2–3 d) of immersion in a 3.5 wt% NaCl solution. σV decreased while σI increased, indicating that the coating became poorly protective. Electrochemical parameters and morphology observation showed that the B72 material itself had poor water resistance. B72 gradually lost its bond with the substrate when exposed to water. The corrosion generated by the pitting holes destroyed the film and led to the development of corrosion (Figure 15b), and the corrosion proceeded slowly even under an intact film layer (Figure 16). In practical applications, it is necessary to keep the surface to be sealed dry and free of water, and the subsequent preservation needs to control the humidity to avoid the formation of liquid film or liquid droplets on the surface of the object when the humidity is too high.

Author Contributions

Conceptualization, H.X., G.H. and S.L.; methodology, H.X. and M.J.; validation, H.X., M.J. and P.H.; investigation, P.H. and M.J.; writing—original draft preparation, H.X.; supervision, H.X. and G.H.; project administration, G.H. and S.L.; funding acquisition, G.H. All authors have read and agreed to the published version of the manuscript.

Funding

This research was funded by the National Key Research and Development Program of China (State assignment No. 2020YFC1522100).

Institutional Review Board Statement

Not applicable.

Informed Consent Statement

Not applicable.

Data Availability Statement

The data presented in this study are available in the article.

Conflicts of Interest

The authors declare no conflicts of interest.

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Figure 1. Different ways of coating the B72 film.
Figure 1. Different ways of coating the B72 film.
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Figure 2. (a) The salt bridge arrangement for ENM; (b) the arrangement for EIS and Polarization curves.
Figure 2. (a) The salt bridge arrangement for ENM; (b) the arrangement for EIS and Polarization curves.
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Figure 3. Time records of (a) the potential and (b) the current of the blank group after de-trending.
Figure 3. Time records of (a) the potential and (b) the current of the blank group after de-trending.
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Figure 4. Time records of (a) the potential and (b) the current of the B72 group after de-trending.
Figure 4. Time records of (a) the potential and (b) the current of the B72 group after de-trending.
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Figure 5. Polarization curves of (a) the blank group and (b) the B72 group at different immersion times.
Figure 5. Polarization curves of (a) the blank group and (b) the B72 group at different immersion times.
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Figure 6. (a) σV and σI of the blank group at different immersion times; (b) Rn and Rp of the blank group at different immersion times.
Figure 6. (a) σV and σI of the blank group at different immersion times; (b) Rn and Rp of the blank group at different immersion times.
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Figure 7. (a) σV and σI of the B72 group at different immersion times; (b) Rn and Rp of the B72 group at different immersion times.
Figure 7. (a) σV and σI of the B72 group at different immersion times; (b) Rn and Rp of the B72 group at different immersion times.
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Figure 8. The blank group’s PSDs of (a) the current and (b) the potential, and (c) Zn at different immersion times.
Figure 8. The blank group’s PSDs of (a) the current and (b) the potential, and (c) Zn at different immersion times.
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Figure 9. The B72 group’s PSDs of (a) the current and (b) the potential, and (c) Zn at different immersion times.
Figure 9. The B72 group’s PSDs of (a) the current and (b) the potential, and (c) Zn at different immersion times.
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Figure 10. The comparison of (a) the current PSD and (b) noise impedance Zn of the two groups at different immersion times (0 d and 6 d).
Figure 10. The comparison of (a) the current PSD and (b) noise impedance Zn of the two groups at different immersion times (0 d and 6 d).
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Figure 11. (a) Impedance modulus and (b) phase of the blank group at different immersion times.
Figure 11. (a) Impedance modulus and (b) phase of the blank group at different immersion times.
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Figure 12. (a) Impedance modulus and (b) phase of the B72 group at different immersion times.
Figure 12. (a) Impedance modulus and (b) phase of the B72 group at different immersion times.
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Figure 13. The noise impedance Zn with impedance modulus of (a) the blank group and (b) the B72 group at different immersion times.
Figure 13. The noise impedance Zn with impedance modulus of (a) the blank group and (b) the B72 group at different immersion times.
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Figure 14. (a) The blank group and (b) the B72 group without immersion.
Figure 14. (a) The blank group and (b) the B72 group without immersion.
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Figure 15. (a) The blank group, (b) the pitting hole, and (c) the wrinkle of the B72 group after immersion.
Figure 15. (a) The blank group, (b) the pitting hole, and (c) the wrinkle of the B72 group after immersion.
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Figure 16. The scanning area and the elemental distribution of the B72 group.
Figure 16. The scanning area and the elemental distribution of the B72 group.
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MDPI and ACS Style

Xu, H.; Jia, M.; Hu, P.; Liu, S.; Hu, G. The Evaluation and Analysis of the Anti-Corrosion Performance of the Sealing Material B72 for Metal Artifacts Based on Electrochemical Noise. Coatings 2024, 14, 1190. https://doi.org/10.3390/coatings14091190

AMA Style

Xu H, Jia M, Hu P, Liu S, Hu G. The Evaluation and Analysis of the Anti-Corrosion Performance of the Sealing Material B72 for Metal Artifacts Based on Electrochemical Noise. Coatings. 2024; 14(9):1190. https://doi.org/10.3390/coatings14091190

Chicago/Turabian Style

Xu, Hao, Minghao Jia, Pei Hu, Shengyu Liu, and Gang Hu. 2024. "The Evaluation and Analysis of the Anti-Corrosion Performance of the Sealing Material B72 for Metal Artifacts Based on Electrochemical Noise" Coatings 14, no. 9: 1190. https://doi.org/10.3390/coatings14091190

APA Style

Xu, H., Jia, M., Hu, P., Liu, S., & Hu, G. (2024). The Evaluation and Analysis of the Anti-Corrosion Performance of the Sealing Material B72 for Metal Artifacts Based on Electrochemical Noise. Coatings, 14(9), 1190. https://doi.org/10.3390/coatings14091190

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