Inhibition of Corrosion of Carbon Steel in Well Water by DL-Phenylalanine-Zn<sup>2+</sup> System

Raja, A. Sahaya; Rajendran, S.; Satyabama, P.

doi:https://doi.org/10.1155/2013/720965

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Volume 2013 | Article ID 720965 | https://doi.org/10.1155/2013/720965

Inhibition of Corrosion of Carbon Steel in Well Water by DL-Phenylalanine-Zn²⁺ System

A. Sahaya Raja,¹S. Rajendran,²and P. Satyabama³

Academic Editor: Hassan Arida

Received26 Dec 2011

Revised14 May 2012

Accepted15 May 2012

Published13 Aug 2012

Abstract

The environmental friendly inhibitor system DL-phenylalanine-Zn²⁺ has been investigated by weight loss method. A synergistic effect exists between DL-phenylalanine and Zn²⁺ system. The formulation consisting of 150 ppm of DL-phenylalanine and 5 ppm of Zn²⁺ offers good inhibition efficiency of 90%. Polarization study reveals that this formulation functions as a anodic inhibitor. AC impedance spectra reveal that a protective film is formed on the metal surface. The surface morphology has been analysed by SEM and EDAX. A suitable mechanism of corrosion inhibition is proposed based on the results obtained from weight loss study and electrochemical studies.

1. Introduction

The use of inhibitor is one of the most practical methods to protect metals from corrosion [1, 2]. Most of the effective inhibitors are compounds containing, in their structures, nitrogen, phosphorus, and/or sulphur. Heteroatoms such as nitrogen, oxygen, and sulphur are capable of forming coordinate covalent bond with metal owing to their free electron pairs and thus, acting as inhibitor [1, 3]. Many researchers were interested in biochemical compounds based on amino acids, which exhibit excellent properties such as good water solubility and rapid biodegradability [4, 5]. These inhibitors used in protection against the corrosion of certain metals such as nickel, cobalt, copper, iron, and steel [6, 7]. The amino acids are the building block of proteins. All amino acids have a central or alpha carbon, to which are bonded four groups; hydrogen, an amino, a carboxyl group, and a unique side chain, also known as R-group [6]. These molecules differ in their unique side chain, which can be used to classify the molecules into functional types. Various amino acids have been used to inhibit the corrosion of metals and alloys [8–17]. The corrosion of mild steel has been inhibited by leucine, alanine and glycine [8], and N,N-bis(phosphonomethyl) glycine (BPMG) [9]. The corrosion of SS 316L has been inhibited by glycine, leucine, valine, and arginine [10]. Cystein, alanine, and phenylalanine have been used to inhibit the corrosion of bronze in an aqueous solution containing sodium sulphate and sodium bicarbonate [11]. Cystein, glycine, glutamic acid, and glutathione have been used as corrosion inhibitor to prevent the corrosion of copper in HCl [12]. The corrosion of brass in O₂-free NaOH has been prevented by methionine [13]. Wilson Sahayaraj et al. have used L-valine along with Zn²⁺ and sodium gluconate to prevent corrosion of carbon steel in rain water [14]. Amin has used glycine derivative to prevent the corrosion of aluminium in KSCN medium [15]. Amino acids have been used to prevent chloride-induced corrosion in reinforced concrete structure [16]. Amino acids such as phenylalanine have been used to prevent corrosion of Mg-Al-Zn alloy in chloride-free neutral solution [17]. The aim of this research is to investigate the inhibitive effect of amino acid such as DL-phenylalanine. For this purpose potentiodynamic polarization and impedance spectroscopy have been used in the present study.

2. Experimental Procedure

2.1. Preparation of Specimens

Carbon steel specimens (0.0267% S, 0.067% P, 0.4% Mn, 0.1% C and the rest iron) of the dimensions 1.0 cm × 4.0 cm × 0.2 cm were polished to mirror finish and degreased with trichloroethylene and used for weight loss method.

2.2. Weight Loss Method

Carbon steel specimens in triplicate were immersed in 100 mL of well water (Table 1) and various concentrations of DL-phenylalanine in the presence and absence of Zn²⁺ (as ZnSO₄7H₂O) for a period of seven days. The corrosion products were cleaned with Clarke’s solution [8]. The weight of the specimens before and after immersion was determined using Shimadzu balance AY62. The corrosion inhibition efficiency was calculated with (1): where is the corrosion rate in the absence of the inhibitor and is the corrosion rate in the presence of inhibitor. From the weight loss, the corrosion rate (mm/y) was calculated: -density of the metal is g/cm³ (7.86).

2.3. Potentiodynamic Polarization Study

Potentiodynamic polarization studies were carried out using a CHI electrochemical impedance analyzer, model 660 A. A three-electrode cell assembly was used. The three-electrode cell assembly is shown in Scheme 1. The working electrode was a rectangular specimen of carbon steel with one face of the electrode (1 cm² area) exposed and the rest shielded with red lacquer. A saturated calomel electrode (SCE) was used as the reference electrode and a rectangular platinum foil was used as the counter electrode. Polarization curves were recorded using iR compensation. The results, such as Tafel slopes, and , , and LPR values were calculated. During the polarization study, the scan rate (v/s) was 0.01, hold time at Ef(s) was zero, and quit time(s) was 2.

2.4. AC Impedance Measurements

A CHI electrochemical impedance analyzer (model 660 A) was used for AC impedance measurements. A time interval of 5 to 10 minutes was given for the system to attain its open circuit potential. The real part Z′ and imaginary part Z′′ of the cell impedance were measured in ohms at various frequencies. The values of the charge transfer resistance , double-layer capacitance , and impedance value were calculated. The equivalent circuit diagram is shown in Scheme 2.

2.5. Scanning Electron Microscopic Studies (SEMs)

The carbon steel specimen immersed in blank and in the inhibitor solution for a period of seven days was removed, rinsed with double-distilled water, dried, and observed in a scanning electron microscope to examine the surface morphology. The surface morphology measurements of the carbon steel were examined using JOEL-6390 computer-controlled scanning electron microscope.

2.6. Energy Dispersive Analysis of X-Rays (EDAXs)

The carbon steel specimen immersed in blank and in the inhibitor solution for a period of seven days was removed, rinsed with double-distilled water, dried, and observed in an Energy Dispersive Analysis of X-Rays (EDAXs) to examine the elements present on the metal surface. The elements present on the metal surface were examined using JOEL-6390 computer-controlled Energy Dispersive Analysis of X-Rays.

3. Result and Discussion

3.1. Analysis of the Weight Loss Method

Corrosion rates (CRs) of carbon steel immersed in well water in the absence and presence of inhibitor (DL-phenylalanine) are given in Tables 2 and 3. The inhibition efficiencies (IE) are also given in these Tables.

It is observed from Table 2 that DL-phenylalanine shows some inhibition efficiencies. 50 ppm of DL-phenylalanine has 41 percent IE. As the concentration of DL-phenylalanine increases, the IE decreases. This is due to the fact that as the concentration of DL-phenylalanine increases, the protective film (probably iron DL-phenylalanine complex) formed on the metal surface goes into solution. That is, the system passes from passive region to active region [9].

3.2. Influence of Zn²⁺ on the Inhibition Efficiencies of DL-Phenylalanine

The influence of Zn²⁺ on the inhibition efficiencies of DL-phenylalanine is given in Table 3. It is observed that as the concentration of DL-phenylalanine increases the IE increases. Similarly, for a given concentration of DL-phenylalanine the IE increases as the concentration of Zn²⁺ increases. It is also observed that a synergistic effect exists between DL-phenylalanine and Zn²⁺. For example, 5 ppm of Zn²⁺ has 15 percent IE; 150 ppm of DL-phenylalanine has 33 percent IE. Interestingly their combination has a high IE, namely, 90 percent.

In presence of Zn²⁺ more amount of DL-phenylalanine is transported towards the metal surface. On the metal surface Fe-DL-phenylalanine complex is formed on the anodic sites of the metal surface. Thus the anodic reaction is controlled. The cathodic reaction is the generation of OH^-, which is controlled by the formation of Zn(OH)₂ on the cathodic sites of the metal surface. Thus, the anodic reaction and cathodic reaction are controlled effectively. This accounts for the synergistic effect existing between Zn²⁺ and DL-phenylalanine:

3.3. Synergism Parameters ()

Synergism parameter () has been used to know the synergistic effect existing between two inhibitors [10–15]. Synergism parameter () can be calculated using the following relationship:

where = surface coverage by DL-phenylalanine, = surface coverage by Zn²⁺, = surface coverage by both DL-phenylalanine and Zn²⁺,where = surface coverage = (IE%)/100.

The synergism parameters of DL-phenylalanine-Zn²⁺ system are given in Table 4. For different concentrations of inhibitors, approaches 1 when no interaction between the inhibitor compounds exists. When , it points to synergistic effects. In the case of , it is an indication that the synergistic effect is not significant [14]. From Table 3, it is observed that values of synergism parameters () calculated from surface coverage were found to be one and above. This indicates that a synergistic effect exists between DL-phenylalanine and Zn²⁺ [12, 13, 15]. Thus, the enhancement of the inhibition efficiency caused by the addition of Zn²⁺ ions to DL-phenylalanine is due to the synergistic effect.

3.4. Analysis of Potentiodynamic Polarization Study (pH = 8)

Polarization study has been used to confirm the formation of protective film formed on the metal surface during corrosion inhibition process [16–21]. If a protective film is formed on the metal surface, the linear polarization resistance value (LPR) increases and the corrosion current value decreases.

The potentiodynamic polarization curves of carbon steel immersed in well water in the absence and presence of inhibitors are shown in Figure 1, the corrosion parameters are given in Table 5. When carbon steel was immersed in well water the corrosion potential was −668 mV versus SCE. When DL-phenylalanine (150 ppm) and Zn²⁺ (5 ppm) were added to the above system, the corrosion potential shifted to the noble side −658 mV versus SCE. This indicates that a film is formed on the anodic sites of the metal surface. This film controls the anodic reaction of metal dissolution by forming Fe²⁺-DL-Phe complex on the anodic sites of the metal surface. The formation of protective film on the metal surface is further supported by the fact that the anodic Tafel slope increases from 104 to 151 mV.

Further, the LPR value increases from 5.630 × 10⁴ ohm cm² to 8.075 × 10⁴ ohm cm²; the corrosion current decreases from A/cm² to A/cm². Thus, polarization study confirms the formation of a protective film on the metal surface.

3.5. Analysis of AC Impedance Spectra

AC impedance spectra (electrochemical impedance spectra) have been used to confirm the formation of protective film on the metal surface [22–24]. If a protective film is formed on the metal surface, charge transfer resistance (R_t) increases, double-layer capacitance value decreases, and the impedance log (z/ohm) value increases. The AC impedance spectra of carbon steel immersed in well water in the absence and presence of inhibitors (DL-phenylalanine-Zn²⁺) are shown in Figures 2(a) and 2(b) (Nyquist plots) and Figures 3(a) and 3(b) and Figures 4(a) and 4(b) (Bode plots). The AC impedance parameters, namely, charge transfer resistance () and double-layer capacitance derived from Nyquist plots are given in Table 6. The impedance log(z/ohm) values derived from Bode plots are also given in Table 6.

(a)

(b)

(a)

(b)

(a)

(b)

It is observed that when the inhibitors [DL-Phe(150 ppm) + Zn²⁺ (5 ppm)] are added, the charge transfer resistance () increases from 1212 Ω cm² to 12711 Ω cm². The value decreases from F/cm² to F/cm². The impedance value [log (z/ohm)] increases from 3.120 to 4.181. These results lead to the conclusion that a protective film is formed on the metal surface.

3.6. SEM Analysis of Metal Surface

SEM provides a pictorial representation of the surface. To understand the nature of the surface film in the absence and presence of inhibitors and the extent of corrosion of carbon steel, the SEM micrographs of the surface are examined [25–27].

The SEM images of different magnification (×500, ×1000) of carbon steel specimen immersed in well water for 7 days in the absence and presence of inhibitor system are shown in Figures 5(a), 5(b), and 5(c), respectively.

(a)

(b)

(c)

The SEM micrographs of polished carbon steel surface (control) in Figure 5(a) show the smooth surface of the metal. This shows the absence of any corrosion products (or) inhibitor complex formed on the metal surface.

The SEM micrographs of carbon steel surface immersed in well water (Figure 5(b)) show the roughness of the metal surface which indicates the highly corroded area of carbon steel in well water. However, Figure 5(c) indicates that in the presence of inhibitor (150 ppm DL-Phe and 5 ppm Zn²⁺) the rate of corrosion is suppressed, as can be seen from the decrease of corroded areas. The metal surface is almost free from corrosion due to the formation of insoluble complex on the surface of the metal [25]. In the presence of DL-Phe and Zn²⁺, the surface is covered by a thin layer of inhibitors which effectively controls the dissolution of carbon steel.

3.7. Energy Dispersive Analysis of X-Rays (EDAXs)

The EDAXs survey spectra were used to determine the elements present on the metal surface before and after exposure to the inhibitor solution [26–29]. The objective of this section was to confirm the results obtained from chemical and electrochemical measurements that a protective surface film of inhibitor is formed on the metal surface. To achieve this, EDAX examinations of the metal surface were performed in the absence and presence of inhibitors system [26–29].

EDAX spectrum of carbon steel immersed in well water is shown in Figure 6(a). They show the characteristic peaks of some of the elements constituting the carbon steel sample. The EDAX spectrum of carbon steel immersed in well water containing 150 ppm of DL-Phe and 5 ppm of Zn²⁺ is shown in Figure 6(b). It shows the additional line characteristic for the existence of N and Zn. In addition, the intensity of C and O signals is enhanced. The appearance of the N and Zn signal and this enhancement in C and O signal is due to the presence of inhibitor. These data show that metal surface covered the N, O, C, and Zn atoms.

(a)

(b)

This layer is undoubtedly due to the inhibitor system. The N, Zn signals and this high contribution of O and C are not present on the metal surface exposed in well water.

Figure 6(b) shows that the Fe peaks observed in the presence of inhibitor are considerably suppressed relative to these observed in well water (blank solution). The suppression of the Fe peaks occurs because of the overlying inhibitor film. This observation indicates the existence of an adsorbed layer of inhibitor that protects steel against corrosion. These results suggest that N, O, and C atoms of DL-phenylalanine have coordinated with Fe²⁺, resulting in the formation of Fe²⁺-DL-Phe complex on the anodic sites of metal surface and presence of Zn atoms is precipitated as Zn(OH)₂ on the cathodic sites of metal surface.

4. Conclusion

Present study leads to the following conclusions. The formulation consisting of 150 ppm of DL-Phenylalanine and 5 ppm of Zn²⁺ offers good inhibition efficiency of 90%. Polarization study reveals that this formulation functions as a anodic inhibitor. AC impedance spectra reveal that a protective film is formed on the metal surface. SEM and EDAX confirm the presence of a protective film on the metal surface.

Acknowledgments

The authors are thankful to their respective management and UGC for their encouragement.

References

N. Hackerman, “The theory and practice of corrosion and its control in industry,” Langmuir, vol. 3, no. 6, pp. 922–924, 1987.
View at: Google Scholar
A. Nestle, “Corrosion inhibitors in petroleum production primary recovery,” in Corrosion Inhibitors, C. C. Nathan, Ed., NACE, Houston, Tex, USA, 1973.
View at: Google Scholar
E. W. Flick, Corrosion Inhibitors: An Industrial Guide, William Andrew, 2nd edition, 1993.
G. Moretti, F. Guidi, and G. Grion, “Tryptamine as a green iron corrosion inhibitor in 0.5 M deaerated sulphuric acid,” Corrosion Science, vol. 46, no. 2, pp. 387–403, 2004.
View at: Publisher Site | Google Scholar
H. Ashassi-Sorkhabi, M. R. Majidi, and K. Seyyedi, “Investigation of inhibition effect of some amino acids against steel corrosion in HCl solution,” Applied Surface Science, vol. 225, no. 1-4, pp. 176–185, 2004.
View at: Publisher Site | Google Scholar
S. Bilgic and A. A. Aksut, “Effect of amino acids on corrosion of cobalt in H₂SO₄,” British Corrosion Journal, vol. 28, no. 1, pp. 59–62, 1993.
View at: Google Scholar
G. Moretti and F. Guidi, “Tryptophan as copper corrosion inhibitor in 0.5 M aerated sulfuric acid,” Corrosion Science, vol. 44, no. 9, pp. 1995–2011, 2002.
View at: Publisher Site | Google Scholar
N. O. Eddy, U. J. Ibok, and B. I. Ita, “QSAR and quantum chemical studies on the inhibition potentials of some amino acids for the corrosion of mild steel in H₂SO₄,” Journal of Computational Methods in Sciences and Engineering, vol. 11, no. 1-2, pp. 25–43, 2011.
View at: Publisher Site | Google Scholar
B. V. A. Rao, M. V. Rao, S. S. Rao, and B. Sreedhar, “Synergistic effect of N,N-Bis(phosphonomethyl) glycine and zinc ions in corrosion control of carbon steel in cooling water systems,” Chemical Engineering Communications, vol. 198, no. 12, pp. 1505–1529, 2011.
View at: Publisher Site | Google Scholar
N. A. Abdel Ghany, A. E. El-Shenawy, and W. A. M. Hussien, “The inhibitive effect of some amino acids on the corrosion behaviour of 316L stainless steel in sulfuric acid solution,” Modern Applied Science, vol. 5, no. 4, pp. 19–29, 2011.
View at: Publisher Site | Google Scholar
S. Varvara, I. Rotaru, M. Popa, and L. M. Mureşan, “Inhibition of bronze corrosion in aerated acidic solution using amino acids as environmentally friendly inhibitors,” Revue Roumaine de Chimie, vol. 56, no. 8, pp. 793–801, 2011.
View at: Google Scholar
D.-Q. Zhang, B. Xie, L.-X. Gao, Q.-R. Cai, H. G. Joo, and K. Y. Lee, “Intramolecular synergistic effect of glutamic acid, cysteine and glycine against copper corrosion in hydrochloric acid solution,” Thin Solid Films, vol. 520, no. 1, pp. 356–361, 2011.
View at: Publisher Site | Google Scholar
J. Wu, Q. Wang, S. Zhang, and L. Yin, “Methionine as corrosion inhibitor of brass in O₂-free 1M NaOH solution,” Advanced Materials Research, vol. 308-310, pp. 241–245, 2011.
View at: Publisher Site | Google Scholar
J. Wilson Sahayaraj, J. Amalraj, and S. Rajendran, “Eco-friendly inhibitor L-valine - Zn²⁺-SG system controlling the corrosion of carbon steel in rain water,” in Proceedings of the International Conference on "Recent Advances in Space Technology Services and Climate Change" (RSTS and CC'10), pp. 247–251, November 2010.
View at: Publisher Site | Google Scholar
M. A. Amin, “A newly synthesized glycine derivative to control uniform and pitting corrosion processes of Al induced by SCN- anions—chemical, electrochemical and morphological studies,” Corrosion Science, vol. 52, no. 10, pp. 3243–3257, 2010.
View at: Publisher Site | Google Scholar
M. Ormellese, F. Bolzoni, L. Lazzari, A. Brenna, and M. Pedeferri, “Organic substances as inhibitors for chloride-induced corrosion in reinforced concrete,” Materials and Corrosion, vol. 62, no. 2, pp. 170–177, 2011.
View at: Publisher Site | Google Scholar
N. H. Helal and W. A. Badawy, “Environmentally safe corrosion inhibition of Mg-Al-Zn alloy in chloride free neutral solutions by amino acids,” Electrochimica Acta, vol. 56, no. 19, pp. 6581–6587, 2011.
View at: Publisher Site | Google Scholar
G. Wranglen, An Introduction to Corrosion and Protection of Metals, Chapman & Hall, New York, NY, USA, 1985.
A. Baral and R. D. Engelken, “Chromium-based regulations and greening in metal finishing industries in the USA,” Environmental Science and Policy, vol. 5, no. 2, pp. 121–133, 2002.
View at: Publisher Site | Google Scholar
A. Y. El-Etre, “Inhibition of aluminum corrosion using Opuntia extract,” Corrosion Science, vol. 45, no. 11, pp. 2485–2495, 2003.
View at: Publisher Site | Google Scholar
A. Y. El-Etre, “Natural honey as corrosion inhibitor for metals and alloys. I. Copper in neutral aqueous solution,” Corrosion Science, vol. 40, no. 11, pp. 1845–1850, 1998.
View at: Publisher Site | Google Scholar
H. Ashassi-Sorkhabi, M. R. Majidi, and K. Seyyedi, “Investigation of inhibition effect of some amino acids against steel corrosion in HCl solution,” Applied Surface Science, vol. 225, no. 1–4, pp. 176–185, 2004.
View at: Publisher Site | Google Scholar
Z. Ghasemi and A. Tizpar, “The inhibition effect of some amino acids towards Pb-Sb-Se-As alloy corrosion in sulfuric acid solution,” Applied Surface Science, vol. 252, no. 10, pp. 3667–3672, 2006.
View at: Publisher Site | Google Scholar
D.-Q. Zhang, L.-X. Gao, and G.-D. Zhou, “Inhibition of copper corrosion in aerated hydrochloric acid solution by amino-acid compounds,” Journal of Applied Electrochemistry, vol. 35, no. 11, pp. 1081–1085, 2005.
View at: Publisher Site | Google Scholar
D. Gopi, S. Manimozhi, K. M. Govindaraju, P. Manisankar, and S. Rajeswari, “Surface and electrochemical characterization of pitting corrosion behaviour of 304 stainless steel in ground water media,” Journal of Applied Electrochemistry, vol. 37, no. 4, pp. 439–449, 2007.
View at: Publisher Site | Google Scholar
M. A. Amin, S. S. Abd El-Rehim, E. E. F. El-Sherbini, and R. S. Bayoumi, “The inhibition of low carbon steel corrosion in hydrochloric acid solutions by succinic acid. Part I. Weight loss, polarization, EIS, PZC, EDX and SEM studies,” Electrochimica Acta, vol. 52, no. 11, pp. 3588–3600, 2007.
View at: Publisher Site | Google Scholar
M. A. Amin, S. S. Abd El Rehim, and H. T. M. Abdel-Fatah, “Electrochemical frequency modulation and inductively coupled plasma atomic emission spectroscopy methods for monitoring corrosion rates and inhibition of low alloy steel corrosion in HCl solutions and a test for validity of the Tafel extrapolation method,” Corrosion Science, vol. 51, no. 4, pp. 882–894, 2009.
View at: Publisher Site | Google Scholar
S. S. A. Rehim, O. A. Hazzazi, M. A. Amin, and K. F. Khaled, “On the corrosion inhibition of low carbon steel in concentrated sulphuric acid solutions. Part I: chemical and electrochemical (AC and DC) studies,” Corrosion Science, vol. 50, no. 8, pp. 2258–2271, 2008.
View at: Publisher Site | Google Scholar
M. A. Migahed, E. M. S. Azzam, and S. M. I. Morsy, “Electrochemical behaviour of carbon steel in acid chloride solution in the presence of dodecyl cysteine hydrochloride self-assembled on gold nanoparticles,” Corrosion Science, vol. 51, no. 8, pp. 1636–1644, 2009.
View at: Publisher Site | Google Scholar

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Copyright © 2013 A. Sahaya Raja et al. This is an open access article distributed under the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

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Journal of Chemistry

Inhibition of Corrosion of Carbon Steel in Well Water by DL-Phenylalanine-Zn2+ System

Abstract

1. Introduction

2. Experimental Procedure

2.1. Preparation of Specimens

2.2. Weight Loss Method

2.3. Potentiodynamic Polarization Study

2.4. AC Impedance Measurements

2.5. Scanning Electron Microscopic Studies (SEMs)

2.6. Energy Dispersive Analysis of X-Rays (EDAXs)

3. Result and Discussion

3.1. Analysis of the Weight Loss Method

3.2. Influence of Zn2+ on the Inhibition Efficiencies of DL-Phenylalanine

3.3. Synergism Parameters ()

3.4. Analysis of Potentiodynamic Polarization Study (pH = 8)

3.5. Analysis of AC Impedance Spectra

3.6. SEM Analysis of Metal Surface

3.7. Energy Dispersive Analysis of X-Rays (EDAXs)

4. Conclusion

Acknowledgments

References

Copyright

Inhibition of Corrosion of Carbon Steel in Well Water by DL-Phenylalanine-Zn²⁺ System

3.2. Influence of Zn²⁺ on the Inhibition Efficiencies of DL-Phenylalanine