Study of corrosion inhibition effect of expired ibuprofen drug on copper in sulfuric acid solution http://dx.doi.org/10.5599/jese.1867 1 J. Electrochem. Sci. Eng. 00(0) (2023) 000-000; http://dx.doi.org/10.5599/jese.1867 Open Access : : ISSN 1847-9286 www.jESE-online.org Original scientific paper Corrosion inhibition effect of expired ibuprofen drug on copper in sulfuric acid solution Said El Harrari, Ayoub Salim, Driss Takky and Youssef Naimi Laboratory of Physical Chemistry of Materials, Faculty of Sciences Ben M’sick, Hassan II University of Casablanca, Morocco Corresponding author: said.elharrari@gmail.com Received: May 2, 2023; Accepted: July 31, 2023; Published: August 7, 2023 Abstract The application of copper as a material in various fields is widely recognized. However, in acidic environments, the electrical and mechanical properties of copper undergo negative alterations, resulting in its dissolution. To protect copper from degradation, the most effective approach is to employ inhibitors. Hence, in this paper, the expired ibuprofen drug has been investigated as a corrosion inhibitor for copper in 0.5 M H2SO4, employing weight loss and electrochemical tests. Compared with the pharmaceutical products used by other researchers in this field, the results showed that ibuprofen is highly effective in protecting copper from corrosion. It was noted that the inhibitory efficacy of ibuprofen increases with concentration. In addition, it was found that its adsorption follows Langmuir isotherm. Keywords Expired drugs; copper corrosion; inhibition efficiency; weight loss; electrochemical tests Introduction Copper is utilized as a conductor in the electronics sector because it is thermally and electrically conductive. Copper can dissolve under certain situations [1], which has detrimental effects on metal characteristics and may result in large financial losses [2]. Therefore, researchers have created a variety of corrosion inhibitors to protect metals and alloys against corroding by acids like sulphuric acid. These blockers are either organic or inorganic compounds [3,4]. In comparison to organic chemicals, particularly azole compounds, inorganic compounds have lower inhibitory effectiveness [5,6]. Many of these substances are poisonous to the environment and therefore, research has been focused on developing waste disposal methods and corrosion inhibitors that are acceptable to the environment. Pharmacological substances [7] are potentially environmentally friendly corrosion inhibitors for copper, according to numerous studies and investigations [8], and pharmaceuticals that are out-of-date or flawed could also be used as conventional inhibitors. Green corrosion inhibitors are natural substances that find application not only in pharmaceutical production [9] but also in plant extraction, which helps to mitigate costs while ensuring the continued availability of http://dx.doi.org/10.5599/jese.1867 http://www.jese-online.org/ mailto:said.elharrari@gmail.com J. Electrochem. Sci. Eng. 00(0) (2023) 000-000 CORROSION INHIBITION EFFECT OF EXPIRED IBUPROFEN DRUG 2 traditional medicines [10]. About 90 % of the medicine's active ingredient remains stable after expi- ration for a long time [11]. Drugs are released into the environment through household garbage [12] and utilizing outdated medications as potential corrosion inhibitors may help lessen environmental pollution. According to studies [13], the pharmaceutical industries are also in charge of getting rid of old medications [14]. Because of this, unused drugs should be carefully eliminated using techniques including photochemical and biodegradation [15,16]. Furthermore, the potential for reusing the medications in corrosion testing would lead to reduced environmental damage from their application. Ibuprofen C13H18O2, (RS)-2-(4-(2-methylpropyl) phenyl) propanoic acid is an anti- inflammatory drug widely used in the treatment of muscle pain in rheumatic diseases. In this paper, the question of whether or not the expired ibuprofen could be used for the effective corrosion inhibition of copper in a sulfuric acid solution (H2SO4), should be clearly answered. Experimental Materials and solution preparation The metal used in this study was copper, with 99 % purity. The metal was covered with epoxy resin to leave a contact surface of 0.5 cm2. The sample was abraded with emery paper (600, 800, 1200, 1500 grad grit) and cleaned with distilled water before each experiment. 0.5 M H2SO4 was prepared using 97 % H2SO4 solution of Sigma-Aldrich. Solutions of ibuprofen inhibitor (Scheme 1) were prepared by dissolving the required amount of ibuprofen powder in H2SO4 solution. To create solutions with decreasing concentrations, the solution with the greatest concentration of 5 mM was diluted to 1, 0.5 and 0.1 mM. In our survey, the expired ibuprofen (stored at a local Moroccan pharmaceutical company's warehouse) was used in the form of drug powder made from ibuprofen tablets of 200 mg. It is known that ibuprofen tablets contain not only ibuprofen compound but also up to 15 % of non-active ingredients such as lactose, starch, microcrystalline cellulose, croscarmellose sodium, colloidal silicon dioxide, polyethylene glycol (PEG) and dyes. This ultimately means that “true” concentrations of ibuprofen were correspondingly lower than declared above. Scheme 1: Chemical structure of ibuprofen C13H18O2 Electrochemical techniques The three-electrode cell and a potentiostat device type PGZ 100, in conjunction with the required VOLTA Master software, were used to carry out electrochemical measurements. A copper electrode with an exposed surface of 0.031 cm2 served as the working electrode, while a standard calomel electrode and a platinum wire as reference and auxiliary electrodes, respectively. The copper electrode was cleaned with distilled water and dried before each measurement. The polarization measurements were recorded in the potential range between -600 mV and 600 mV with a sweep rate of 1 mV/s after a stabilization time of 40 minutes. S. El Harrari et al. J. Electrochem. Sci. Eng. 00(0) (2023) 000-000 http://dx.doi.org/10.5599/jese.1867 3 Electrochemical impedance measurements (EIS) were carried out at the constant OCP in the frequency range of 100 kHz to 10 mHz, under potentiostatic conditions using the alternating signal with the amplitude of 10 mV peak-to-peak. The values of electrochemical parameters were extracted using EC-LAB software. Weight loss measurements Copper samples of size 75×13×3 mm were used in the weight loss experiments. These samples were immersed in 0.5 M H2SO4 sulfuric acid solutions in the absence and presence of 5 mM ibuprofen for 10 days at room temperature. Each sample was washed with distilled water and then weighed on a PA214 analytical balance with a weighing accuracy of 0.0001 g. Analysis of copper surfaces by scanning electron microscopy In order to confirm the protective properties of ibuprofen, the surfaces of copper samples subjected previously to different acid solutions for 10 days were analyzed using a Hirox SH4000M scanning electron microscope. The copper samples were prepared for weight loss measurements. Results and discussion Polarization potentiometric measurements The potentiodynamic polarization curves for copper in 0.5 M H2SO4 without and with the addition of an expired ibuprofen inhibitor are shown in Figure 1. Figure 1. Potentiodynamic polarization curves of copper in 0.5 M H2SO4 solution without and with the addition of ibuprofen It is evident that the corrosion current density (jcorr) decreased in the presence of the expired drug. The corrosion potential (Ecorr) of the inhibited media is shifted in the positive direction compared to the Ecorr of the blank solution. The change in Ecorr in the inhibited solutions is more than 85 mV, compared to the value of Ecorr in the blank solution, which suggests that ibuprofen can be classified as an anodic type inhibitor [17]. On the other side, parallel cathodic Tafel lines show that the presence of an ibuprofen inhibitor has little impact on the cathodic reaction [18]. The data for corrosion potentials as well as corrosion current densities, anodic (ba) and cathodic (bc) Tafel slopes, and inhibition efficiencies (IE), are presented in Table 1. -600 -400 -200 0 200 400 600 -6 -5 -4 -3 -2 -1 0 1 2 3 lo g j / m A c m -2 Potential, mV Blank H2SO4 + 10 -4 inh H2SO4 + 5*10 -4 inh H2SO4 + 10 -3 inh H2SO4 + 5*10 -3 inh lo g ( j / m A c m -2 ) http://dx.doi.org/10.5599/jese.1867 J. Electrochem. Sci. Eng. 00(0) (2023) 000-000 CORROSION INHIBITION EFFECT OF EXPIRED IBUPROFEN DRUG 4 Table 1 . Electrochemical parameters of copper corrosion in 0.5M H2SO4 solution without and with addition of different concentrations of ibuprofen Inhibitor concentration, mM Ecorr / mV jcorr /μA cm-2) ba / mV decade-1 bc / mV decade-1 IE, % 0.0 -309 171.40 93.4 -83.9 --- 0.1 -84 30.56 167.8 -241.9 82.17 0.5 -117 24.59 117.6 -219.4 85.65 1.0 -244.6 13.80 219.0 -89.2 91.95 5.0 -235.5 8.89 136.6 -81.4 94.81 According to Table 1, the addition of the inhibitor changed the values of ba and bc as a result of the inhibitor molecules adhering to the metal surface to form a protective layer [19]. Also, adding ibuprofen to sulphuric acid caused a drop in current density values, and this behavior continuously takes place as ibuprofen concentration rises. This demonstrates that under these circumstances, ibuprofen can shield copper surface. The inhibitor efficiency (IE, %) values of the expired ibuprofen were determined by Eq. (1) [20]: IE = ((jcorr−jcorr(inh)) / jcorr) 100 (1) where jcorr and jcorr(inh) are corrosion current densities in the absence and presence of the inhibitor, respectively. It is clearly seen in Table 1 that the inhibitor concentration affects inhibitor efficiency, which is connected to the adsorption of inhibitor molecules on the copper surface. Furthermore, ibuprofen was found to be an efficient inhibitor for copper corrosion in the studied medium as the inhibition effectiveness reached even 94.81 % at 5 mM. Electrochemical impedance spectroscopy Electrochemical impedance spectroscopy experiments were carried out to further examine the impact of ibuprofen on copper corrosion behavior. The outcomes are displayed in Figure 2 in the form of Nyquist plots (-Zi vs. Zr). By analyzing the Nyquist diagrams in Figure 2, it is evident that when the inhibitor concentration rises, so does the diameter of an obtained semicircle, suggesting a decrease in the corrosion rate of the Cu sample [21]. Additionally, a small contribution of the Warburg impedance is seen at the lowest frequencies, indicating diffusion processes, such as diffusion of soluble copper species or dissolved oxygen on the copper surface [22]. Figure 2: Nyquist plots for copper in 0.5M H2SO4 in the absence and presence of different concentrations of ibuprofen 0 2000 4000 6000 8000 10000 12000 14000 0 2000 4000 6000 8000 10000 12000 14000 -Z i / W c m 2 Zr / W cm 2 blank H2SO4 + 10 -4 inh H2SO4 + 5*10 -4 inh H2SO4 + 10 -3 inh H2SO4 + 5*10 -3 inh https://www.nature.com/articles/s41598-019-51299-2#Tab1 S. El Harrari et al. J. Electrochem. Sci. Eng. 00(0) (2023) 000-000 http://dx.doi.org/10.5599/jese.1867 5 The EC-Lab software program and the equivalent circuit shown in Figure 3 were used to fit the experimental data, where Rs is the solution resistance, Rf is the resistance of the protective inhibitor film formed on the copper surface, Rct is the charge transfer resistance of corrosion, while Qf and Qdl represent constant phase elements (CPE). CPEs are put instead of pure capacitors, Cf, for the film capacitance and Cdl for the capacitance of the double layer. W is the Warburg (diffusion) impedance and n is the deflection parameter. The parameters Cf and Cdl were calculated according to the equations (2) and (3): Cf = (QfRf1-n1)1/n1 (2) Cdl = (QdlRct1-n2)1/n2 (3) The calculated capacitance values and other impedance parameter values obtained by curve fitting of the electric equivalent circuit (EEC) in Figure 3 to impedance plots in Figure 2 are listed in Table 2 for different concentrations of ibuprofen. Figure 3: Equivalent electrical circuit for copper in sulphuric acid solution in the absence and presence of different concentrations of ibuprofen Table 2. Electrochemical impedance parameters for copper in 0.5 M H2SO4 solution without and with ibuprofen added Inhibitor concentration, M Rs / Ω cm2 Cf / F cm−2 n1 Rf / Ω cm2 Cdl / F cm−2 n2 Rct / Ω cm2 W0 / Ω−1 cm−2 s0.5 Rp = Rs + Rct / Ω cm2 IE, % Blank 1.192 0.52×10-3 0.72 399.6 7.21×10-3 0.53 221.4 0.38 621 --- 10−4 7.522 1.49×10-6 0.97 241.1 13.98×10-6 0.57 7 561 / 7 802 92.04 5×10−4 9.475 2.64V10-6 0.93 733.7 16.85×10-6 0.49 9 675 / 10 409 94.03 10−3 7.260 1.97×10-6 0.96 256.6 13.75×10-6 0.53 11 965 / 12 222 94.91 5×10−3 9.772 2.78×10-6 0.93 989 16.16×10-6 0.48 12 107 / 13 096 95.25 According to the results presented in Table 2, the increased values of Rct in the presence of the ibuprofen inhibitor indicate slower rates of copper corrosion, probably due to the increase in surface homogeneity due to inhibitor adsorption. Furthermore, as the inhibitor concentration increased, the values of Cf and Cdl decreased. This is related to the adsorption of inhibitor molecules on the copper surface, which reduces the surface area of copper exposed to aggressive ions. According to the obtained results, it is assumed that the copper surface is uniformly coated. The following equation was used to compute the inhibitory efficiency: IE = [(Rp – Rp0) / Rp] 100 (4) where Rp0 is the polarization resistance of the copper electrode in the blank solution and Rp is the polarization resistance of the studied medium in the presence of the inhibitor. Note that polarization resistance Rp is defined as Rp = Rf + Rct. Rp values are also listed in Table 2. It can be seen that the computed IE values from EIS shown in Table 2 and from potentiodynamic polarization shown in Table 1 are in relatively good agreement. http://dx.doi.org/10.5599/jese.1867 J. Electrochem. Sci. Eng. 00(0) (2023) 000-000 CORROSION INHIBITION EFFECT OF EXPIRED IBUPROFEN DRUG 6 More about the interactions at the adsorbate/substrate interface may be obtained by the analysis of adsorption isotherms [23]. Various adsorption isotherms were tested, and it was shown that the Langmuir adsorption isotherm, with a linear regression coefficient (R2) equal to unity and a slope approaching unity, is the best representative for the inhibitor adsorption (Figure 4). Figure 4. Langmuir adsorption isotherm for the adsorption of ibuprofen on copper surface Equation (5) yields the Langmuir isotherm formula: inh inh ads 1C C K = + (5) where  is the surface fraction covered by adsorbed species, and Kads is the equilibrium adsorption constant (M-1). By using Figure 5 and eq. (5), the adsorption equilibrium constant was determined as Kads = 1.897 mM-1. Adsorption free energy change (G0ads) value was calculated using equation (6): G0ads = -RT ln (55.4 Kads) (6) Herein, R is the universal gas constant, and T is the absolute temperature. The computed adsorption free energy value is G0ads= -40 kJ mol-1, which means the process is spontaneous. Since the value of G is -40 kJ mol-1, we can say that the adsorption of ibuprofen on the copper surface takes place via physicochemical adsorption [24]. Figure 5. Weight loss curves for copper in 0.5 M H2SO4 solution without and with addition of ibuprofen; ⎯ copper in H2SO4, ⎯ copper in H2SO4 with 5 mM of inhibitor 0.000 0.001 0.002 0.003 0.004 0.005 0.000 0.001 0.002 0.003 0.004 0.005 0.006 C  -1 / M C / M 22.615 22.620 22.625 22.630 22.635 22.640 22.645 22.650 1 2 3 4 5 6 7 8 9 10 11 M a ss o f co p p e r, g Number of day C  - 1 / M S. El Harrari et al. J. Electrochem. Sci. Eng. 00(0) (2023) 000-000 http://dx.doi.org/10.5599/jese.1867 7 Weight loss measurements Figure 5 shows a decrease of the copper mass during immersion in 0.5 M H2SO4 without and with 0.5 mM of ibuprofen inhibitor. It is obvious, that the mass of the copper is less decreased once the inhibitor is added to the sulfuric acid [25]. In the absence of the inhibitor, the gravimetric test of copper immersed in sulfuric acid reveals a significant weight loss due to the aggression of the acid, but with the addition of 5 mM ibuprofen, the metal undergoes a much slower attack. Surface characterization by SEM SEM was used to characterize the surfaces of copper coupons subjected to 0.5 M H2SO4 in the presence and absence of the highest concentration of ibuprofen (5 mM). The coupons were submerged in solutions for 10 days at room temperature, as for weight loss measurements in Figure 5, and the resulting SEM micrographs are shown in Figure 6. In contrast to the pitting and cracking that were found in the solution without the inhibitor, it has been noticed that the copper surface is smoother in the presence of the inhibitor. This can be the effect of ibuprofen forming a thick film on the metal surface. (a) (b) (c) Figure 6. SEM images of the copper surface in the initial state (a), and after 10 days of immersion in 0.5 M H2SO4 solution without inhibitor (b) and with 5 mM ibuprofen (c) Conclusions The expired ibuprofen drug was tested as a possible corrosion inhibitor of copper in the sulfuric acid solution, showing that the ibuprofen product can efficiently protect copper surfaces. The data showed that as the inhibitor concentration rises, the effectiveness of inhibition also rises, attaining about 95 % at the highest ibuprofen concentration of 5 mM. Ibuprofen is classified as an anodic type of corrosion inhibitor, which acts by forming a protective film on the copper surface. The development of a protective film was supported by SEM analysis of copper surfaces after immersion in sulfuric acid containing ibuprofen. References [1] Yu.I. Kuzntesov, I.A. Kuznetsov, N.P. Andreeva, Adsorbtion of sodium tridecanoate on copper from aqueous solutions and copper protection from atmospheric corrosion, The International Journal of Corrosion and Scale Inhibition 7 (2018) 650-658. https://doi.org/10.17675/2305-6894-2018-7-4-11 [2] M. Finšgar, I. Milošev, Inhibition of copper corrosion by 1,2,3-benzotriazole: A review, Corrosion Science 52 (2010) 2737-2749. https://doi:10.1016/j.corsci.2010.05.002 [3] S. Cao, R. Cheng, H. Liu, W. Shi, Q. Yuan, J. Chen, Comparative studies of three isatin-thi- osemicarbazones against corrosion of AA6060 aluminum alloy exposed to acidic NaCl medium, Journal of Molecular Structure 1269 (2022) 133835. https://doi.org/10.1016/ j.molstruc.2022.133835 http://dx.doi.org/10.5599/jese.1867 https://doi.org/10.17675/2305-6894-2018-7-4-11 https://www.sciencedirect.com/author/7004921683/ingrid-milosev https://www.sciencedirect.com/journal/corrosion-science/vol/52/issue/9 https://doi.org/10.1016/‌j.molstruc.2022.133835 https://doi.org/10.1016/‌j.molstruc.2022.133835 J. Electrochem. Sci. Eng. 00(0) (2023) 000-000 CORROSION INHIBITION EFFECT OF EXPIRED IBUPROFEN DRUG 8 [4] M. Galai, J. Ouassir, M. Ebn Touhami, H. Nassali, H. Benqlilou, T. Belhaj, K. Berrami, I. Mansouri, B. Oauki, α-Brass and (α+ β) Brass Degradation Processes in Azrou Soil Medium Used in Plumbing Devices, Journal of Bio-and Tribo-Corrosion 3 (2017) 30. https://doi.org/ 10.1007/s40735-017-0087-y [5] G. Tansuğ, T. Tüken, E.S. Giray, G. Fındıkkıran, G. Sığırcık, O. Demirkol, M. Erbil, A new corrosion inhibitor for copper protection, Corrosion Science 84 (2014) 21-29. http://dx.doi.org/10.1016/j.corsci.2014.03.004 [6] I.G. Akande, O.S.I. Fayomi, O.J. Adelakun, Evaluation of inhibitive performance of ibuprofen drug on copper in 0.5 M H2SO4, Case Studies in Chemical and Environmental Engineering, 2 (2020) 100024. https://doi:10.1016/j.cscee.2020.100024 [7] V. Nemane, S. Chatterjee, Evaluation of microstructural, mechanical, and tribological charac- teristics of Ni-B-W-SiC electroless composite coatings involving multi-pass scratch test, Materials Characterization 180 (2021) 111414. https://doi.org/10.1016/j.matchar.2021.11 1414 [8] H. Ma, S. Chen, B. Yin, S. Zhao, X. Liu, Impedance spectroscopic study of corrosion inhibition of copper by surfactants in the acidic solutions, Corrosion Science 45 (2003) 867-882. https://doi.org/10.1016/S0010-938X(02)00175-0 [9] A. Biswas, S. K. Das, P. Sahoo, Oxidation issues during heat treatment and effect on the tribo- mechanical performance of electroless Ni-P-Cu deposits, Proceedings of the Institution of Mechanical Engineers, Part L: Journal of Materials: Design and Applications 235 (2021) 1661- 1685. https://doi.org/10.1177%2F1464420721999823 [10] M. Fuseini, M. Mahmoud, Y. Zaghloul, M. F. Elkady, A. H. El-Shazly, Evaluation of synthesized polyaniline nanofibres as corrosion protection film coating on copper substrate by electrophoretic deposition, Journal of Materials Science 57 (2022) 6085-6101. https://doi.org/10.1007/s10853-022-06994-3 [11] J.B. Matos, L.P. Pereira, S.M.L. Agostinho, O.E. Barcia, G.G.O. Cordeiro, E. D’Elia, Effect of cysteine on the anodic dissolution of copper in sulfuric acid medium, Journal of Electroanalytical Chemistry 570 (2004) 91-94. https://doi:10.1016/j.jelechem.2004.03.020 [12] A. Biswas, S. K. Das, P. Sahoo, Investigation of the tribological behavior of electroless Ni-W-P coating pre and post phase transformation regime, Materials Research Express 6 (2019) 0965c1. https://doi.org/10.1088/2053-1591/ab33bd [13] J. Núñez-Morales, L. I. Jaramillo, P. J. Espinoza-Montero, V. E. Sánchez-Moreno, Evaluation of Adding Natural Gum to Pectin Extracted from Ecuadorian Citrus Peels as an Eco-Friendly Corrosion Inhibitor for Carbon Steel, Molecules 27 (2022) 2111. https://doi.org/10.3390/ molecules27072111 [14] L. Guo, I. B. Obot, X. Zheng, X. Shen, Y. Qiang, S. Kaya, C. Kaya, Theoretical insight into an empirical rule about organic corrosion inhibitors containing nitrogen, oxygen, and sulfur atoms, Applied Surface Science 406 (2017) 300-310. https://doi.org/10.1016/j.apsusc.20 17.02.134 [15] S. C. Ikpeseni, G. O. Odu, H. I. Owamah, P. U. Onochie, D. C. Ukala, Thermodynamic parameters and adsorption mechanism of corrosion inhibition in mild steel using jatropha leaf extract in hydrochloric acid, Arabian Journal for Science and Engineering 46 (2021) 7789- 779. https://doi.org/10.1007/s13369-021-05488-9 [16] Z.Z. Tasić, M.B. Petrović Mihajlović, A.T. Simonović, M.B. Radovanović, M.M. Antonijević, ibuprofen as a corrosion inhibitor for copper in synthetic acid rain solution, Scientific Reports 9 (2019) 14710. https://doi:10.1038/s41598-019-51299-2 [17] Y. Yu, D. Yang, D. Zhang, Y. Wang, L. Gao, Anti-corrosion film formed on HAl77-2 copper alloy surface by aliphatic polyamine in 3 wt.% NaCl solution, Applied Surface Science 392 (2017) 768-776. http://dx.doi.org/10.1016/j.apsusc.2016.09.118 https://doi.org/‌10.1007/s40735-017-0087-y https://doi.org/‌10.1007/s40735-017-0087-y http://dx.doi.org/10.1016/j.corsci.2014.03.004 https://www.sciencedirect.com/journal/case-studies-in-chemical-and-environmental-engineering/vol/2/suppl/C https://doi.org/10.1016/j.matchar.2021.11‌1414 https://doi.org/10.1016/j.matchar.2021.11‌1414 http://dx.doi.org/10.1016/S0010-938X(02)00175-0 https://doi.org/10.1177%2F1464420721999823 https://doi.org/10.3390/‌molecules27072111 https://doi.org/10.3390/‌molecules27072111 https://doi.org/10.1016/j.apsusc.20‌17.02.134 https://doi.org/10.1016/j.apsusc.20‌17.02.134 https://doi.org/10.1007/s13369-021-05488-9 http://dx.doi.org/10.1016/j.apsusc.2016.09.118 S. El Harrari et al. J. Electrochem. Sci. Eng. 00(0) (2023) 000-000 http://dx.doi.org/10.5599/jese.1867 9 [18] Y. Gan, M. Zhou, C. Ji, G. Huang, Y. Chen, L. Li, T. Huang, Y. Lu, J. Lin, Tailoring the tribology property and corrosion resistance of selective laser melted CoCrMo alloys by varying copper content, Materials & Design 228 (2023) 111869. https://doi.org/10.1016/j.matdes.2023.11 1869 [19] R. Moaref, M. H. Shahini, H. E. Mohammadloo, B. Ramezanzadeh, S. Yazdani, Application of sustainable polymers for reinforcing bio-corrosion protection of magnesium implants–a review, Sustainable Chemistry and Pharmacy 29 (2022) 100780. https://doi.org/10.1016/ j.scp.2022.100780 [20] A. I. Abou-Sreea, M. H. Roby, H. A. Mahdy, N. M. Abdou, A. M. El-Tahan, M. T. El-Saadony, K. A. El-Tarabily, F. M. El-Saadony, Improvement of Selected Morphological, Physiological, and Biochemical Parameters of Roselle (Hibiscus sabdariffa L.) Grown under Different Salinity Levels Using Potassium Silicate and Aloe saponaria Extract, Plants 11 (2022) 497. https://doi.org/10.3390/plants11040497 [21] O. A. Elgyar, A. M. Ouf, A. El-Hossiany, A. S. Fouda, The inhibition action of viscum album extract on the corrosion of carbon steel in hydrochloric acid solution, Biointerface Research in Applied Chemistry 11 (2021) 14343-14350. https://doi.org/10.33263/BRIAC116.143441 4358 [22] M. Finšgar, D. K. Merl, An electrochemical, long-term immersion, and XPS study of 2- mercaptobenzothiazole as a copper corrosion inhibitor in chloride solution, Corrosion Science 83 (2014) 164-175. http://dx.doi.org/10.1016/j.corsci.2014.02.016 [23] H. Cao, M. Fang, W. Jia, X. Liu, Q. Xu, Remarkable improvement of corrosion resistance of silane composite coating with Ti3C2Tx MXene on copper, Composites 228 (2022) 109427. https://doi.org/10.1016/j.compositesb.2021.109427 [24] M.E. Belghiti , Y. El Oudadi , S. Echihi , A. Elmelouky , H. Outada ,Y. Karzazi , M. Bakasse , C. Jama , F. Bentiss , A. Dafali, Anticorrosive properties of two 3,5-dissubstitud-4-amino-1,2,4- triazole derivatives on copper in hydrochloric acid environment: Ac impedance, thermodynamic and computational investigations, Surfaces and Interfaces 21 (2020) 100692. https://doi.org/10.1016/j.surfin.2020.100692 [25] M. Belhadi, M. Oubahou, I. Hammoudan, A. Chraka, M. Chafi, S. Tighadouini, A comprehensive assessment of carbon steel corrosion inhibition by 1,10-phenanthroline in the acidic environment: insights from experimental and computational studies, Environmental Science and Pollution Research (2023). https://doi.org/10.1007/s11356-023- 27582-1 ©2023 by the authors; licensee IAPC, Zagreb, Croatia. This article is an open-access article distributed under the terms and conditions of the Creative Commons Attribution license (https://creativecommons.org/licenses/by/4.0/) http://dx.doi.org/10.5599/jese.1867 https://www.sciencedirect.com/journal/materials-and-design https://www.sciencedirect.com/journal/materials-and-design/vol/228/suppl/C https://doi.org/10.1016/j.matdes.2023.11‌1869 https://doi.org/10.1016/j.matdes.2023.11‌1869 https://doi.org/10.1016/‌j.scp.2022.100780 https://doi.org/10.1016/‌j.scp.2022.100780 https://doi.org/10.33263/BRIAC116.143441‌4358 https://doi.org/10.33263/BRIAC116.143441‌4358 http://dx.doi.org/10.1016/j.corsci.2014.02.016 https://www.sciencedirect.com/author/7403744157/qunjie-xu https://www.sciencedirect.com/journal/composites-part-b-engineering https://www.sciencedirect.com/journal/composites-part-b-engineering/vol/228/suppl/C https://doi.org/10.1016/j.compositesb.2021.109427 https://doi.org/10.1016/j.surfin.2020.100692 https://doi.org/10.1007/s11356-023-27582-1 https://doi.org/10.1007/s11356-023-27582-1 https://creativecommons.org/licenses/by/4.0/)