Use of Rosa canina fruit extract as a green corrosion inhibitor for mild steel in 1 M HCl solution: A complementary experimental, molecular dynamics and quantum mechanics investigation

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Highlights

  • Rosa canina fruit extract was used as a green corrosion inhibitor for mild steel corrosion inhibition in 1 M HCl.

  • Rosa canina fruit extract acted as a mixed type inhibitor and significantly reduced the mild steel corrosion rate in 1 M HCl.

  • Theoretical studies revealed the Rosa canina inhibitors adsorption to mild steel via electron-transfer interactions.

Abstract

Rosa canina fruit extract was utilized for mild steel corrosion inhibition in 1 M HCl solution. The inhibition efficiency of inhibitor was studied by electrochemical impedance spectroscopy (EIS) and potentiodynamic polarization test. Results revealed that R. canina fruit extract acted as a mixed type inhibitor and remarkably reduced the corrosion current density of mild steel from 110 μA/cm2 (0 ppm) to 44 μA/cm2 (800 ppm). The maximum corrosion inhibition efficiency (about 86%) was obtained using 800 ppm inhibitor. The inhibitor adsorption on the mild steel surface significantly increased the water contact angle (about 50%).

Introduction

Nowadays, mild steel is known as the most famous alloy in a wide range of industrial applications such as metal processing, equipment and construction. Acid cleaning treatments by means of HCl solution is often applied for removing the scales, oxides and surface impurities from the surface of mild steel in a wide range of industrial applications [1], [2]. Consequently, it is necessary to control the severe dissolution rate of iron during exposure to acidic environments. One effective approach for reducing the iron dissolution rate during acid treatment is the addition of small quantities of organic and/or inorganic corrosion inhibitors to the acid solution. Most of the organic corrosion inhibitors contain functional groups with heteroatoms like O, N or S and/or π electrons in conjugated double bonds. The corrosion inhibition performance of an inhibitor depends on the type of interactions between inhibitors and metal surface [3], [4], [5], [6], [7], [8], [9], [10].

In the last decade the corrosion inhibition effects of a large number of inorganic (such as chromate, molybdate and phosphate) [11] and organic (such as triazoles, imidazoles, amino acids, phenothiazine, and Schiff bases) [12], [13], [14], [15], [16] corrosion inhibitors have been studied. Although these corrosion inhibitors are effective but most of them are toxic and expensive. Recently, the usage of such toxic corrosion inhibiting materials which are harmful for human health and ecosystem has been strongly prohibited by various international agencies. Instead, the green compunds has attracted the resaearchers’ attention [17], [18], [19], [20], [21], [22].

The researchers’ attention has been recently directed towards the use of green corrosion inhibitors obtained from the plant sources. Most of the natural organic compounds are environmentally acceptable and effective corrosion inhibitors for metals in acidic media. The organic compounds existed in the plant roots, leaves and seeds, such as alkaloids, flavonoids, amino acids and proteins, include many aromatic rings and functional N, S or O containing groups. As a result, they can interact with metal surface and show high degree of corrosion inhibition [23]. Alvarez et al. [24] studied the mild steel corrosion inhibition in 1 M HCl solution containing Rollinia occidentalis extract. They found that in the presence of R. occidentalis extract the mild steel corrosion rate considerably decreased. In addition, the inhibitor adsorption on the mild steel surface obeyed a Langmuir adsorption isotherm by affecting both anodic and cathodic reactions. In our recent study [25], the effect of Glycyrrhiza glabra extract on the mild steel corrosion in HCl acidic media was investigated by experimental and theoretical methods. The results demonstrated that in the presence of G. glabra extract the corrosion rate of mild steel significantly decreased. Inhibition efficiency of 88% and surface coverage of 72% were obtained for this inhibitor.

By applying the Nicotiana tabacum leaves extract for mild steel corrosion in 2 M H2SO4 media Bhawsar et al. [26] found that the inhibitor adsorption on the mild steel surface obeyed a Langmuir’s adsorption isotherm. It was also shown that in the presence of N. tabacum leaves extract the corrosion rate significantly decreased. In another study, Deyab et al. [27] assessed the corrosion of copper in HCl solution containing Egyptian licorice extract. Results proved that the Egyptian licorice extract behaved as a mixed-type inhibitor and its adsorption on the copper surface followed a Temkin adsorption isotherm. Odewunmi et al. [28] investigated the effect of Watermelon rind extract on the mild steel corrosion inhibition in an acidic medium. These authors observed that in the presence of green inhibitor based on Watermelon rind extract the corrosion rate of mild steel in HCl and H2SO4 solutions significantly reduced. The inhibitor showed mixed anodic and cathodic inhibition effects, following a Temkin adsorption isotherm model. In the current study, it was intended to investigate the inhibition effect of a green corrosion inhibitor based on Rosa canina fruit extract on mild steel corrosion in 1 M HCl solution by using electrochemical impedance spectroscopy and polarization tests. Furthermore, to examine the adsorption of inhibitor on the steel substrate and the active sites of inhibitor influencing its adsorption characteristics the theoretical molecular dynamics (MD) simulations and quantum mechanics (QM) computations were applied.

Section snippets

Raw materials and sample preparation

R. canina fruit was obtained from north coast of Iran. The dried R. canina fruit was dried and powdered. Then, 25 g R. canina fruit powder was added to 500 ml distilled deionized water and mixed for 24 h at 70 °C and then the extract was filtered and dried at 60 °C for 3 h. The steel sheets (10 cm × 8 cm × 0.2 cm) with chemical composition (wt.%) of: 0.04% Al, 0.05% P, 0.05% S, 0.19% C, 0.32% Mn, 0.34% Si, and 99.01% Fe were prepared from Foolad Mobarakeh Co. (Iran). Analytical grade of HCl (37%) was

Quantum mechanics methodology

Before performing all-atom MD simulations, the ab initio QM techniques were applied to recognize the global minimum energy geometries of organic green inhibitors of ascorbic acid, marein, pectin and tannin. Fig. S1 in Supporting information depicts the neutral structures of these corrosion inhibiting compounds. As the electron-donor or basic oxygen heteroatoms could become protonated in acidic environments, these corrosion inhibiting compounds likely coexist in neutral and protonated states

R. canina fruit extract characterization

The UV–vis absorption spectra were obtained for the HCl solutions with 800 ppm inhibitors before and after immersion of steel specimen (Fig. 1(a)). According to Fig. 1, the UV–vis spectra include two characteristic absorption peaks around 208–210 nm and 274 nm. The sharp absorption peak centered at 208–210 nm is attributed to the π–π* transitions of the Cdouble bondC bonds of aromatic ring [58] and the less intensive peak appeared at around 274 nm is attributed to the transition of n–π* of functional groups

Conclusions

  • Results obtained from EIS analysis revealed that with the increase of inhibitor concentration up to 800 ppm and the immersion time up to 24 h the polarization resistance, surface coverage and inhibition efficiency significantly increased.

  • The polarization test results showed that the R. canina fruit extract acted as a mixed type inhibitor and reduced both anodic dissolution rate of iron and cathodic hydrogen evolution reaction rate. It was shown that in the presence of inhibitor the anodic

Acknowledgment

The authors gratefully thank the use of School of Computer Science, Institute for Research in Fundamental Science (IPM) as the computations were done there.

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