Corrosion Science 51 (2009) 27902793

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Corrosion Science
journal homepage: www.elsevier.com/locate/corsci

Short Communication

The effects of Phyllanthus amarus extract on corrosion and kinetics of corrosion process of aluminum in alkaline solution
Olusegun K. Abiola a,b,*, J.O.E. Otaigbe c
a

Department of Chemistry, Federal University of Petroleum Resources, Effurum, Nigeria Department of Chemistry, University of Lagos, Lagos, Nigeria c Department of Pure and Industrial Chemistry, University of Port Harcourt, Port Harcourt, Nigeria
b

a r t i c l e

i n f o

a b s t r a c t
The effect of the extract of Phyllanthus amarus leaves on the corrosion of aluminum in 2 M NaOH solution was studied using chemical technique. The extract acts as corrosion inhibitor, with 76% efciency at the highest concentration in the alkaline environment and the inhibition efciency increased with increasing concentration of the extract. The adsorption of the inhibitor on aluminum surface was in accordance with the Langmuir adsorption isotherm. A zero-order kinetics relationship with respect to aluminum was obtained with and without the extract from the kinetics treatment of the data. 2009 Elsevier Ltd. All rights reserved.

Article history: Received 21 May 2009 Accepted 4 July 2009 Available online 9 July 2009 Keywords: A. Aluminum Phyllanthus amarus B. Weight loss C. Alkaline corrosion Kinetics

1. Introduction Organic and inorganic compounds [113] are widely used as corrosion inhibitors to control the dissolution of the protective oxide lm on the surface of aluminum in alkaline solution; in order to minimize metal loss and the consumption of the alkaline solution. Thus, organic and inorganic compounds are usually added to alkaline media as corrosion inhibitors in industrial processes such as alkaline cleaning, pickling and etching, and to improve efciency in devices such as aluminum alkaline battery [2,8]; but some of these inhibitors are toxic, expensive and non-biodegradable. Consequently; attention has been focused on plant extracts as substitutes to toxic and non-biodegradable corrosion inhibitors due to increasing environmentally awareness. This is because plant extracts are environmentally friendly, inexpensive, readily available and renewable sources of materials [1,1418]. Several plant extracts have been reported as inhibitors for different metals in alkaline or acid solutions [1,1423]. More recently [1], we reported the inhibition of aluminum corrosion in NaOH solution in presence of Gossipium hirsutum L. extracts and that the organic compounds in the extracts establish their inhibition via adsorption of their molecules on the metal surface forming a protective barrier.

In previous work [23], Phyllanthus amarus extract was found to inhibit the corrosion of mild steel in acid solutions using chemical technique. P. amarus contains several biodegradable ecologically friendly organic compounds [2328] and these compounds can be extracted by simple procedure. Literature search reveals that no study has been done on the inhibitive effects of P. amarus extract on alkaline corrosion of aluminum. Therefore, we consider it necessary to study the effects of P. amarus extract on alkaline corrosion of aluminum in sodium hydroxide solution. In the present study, the effect of P. amarus extract on both the corrosion and kinetics of corrosion process of aluminum in 2 M sodium hydroxide solution have been investigated using weight loss measurements. 2. Experimental 2.1. Material preparations The chemical composition and the preparation of 3SR aluminum alloy specimens (4 2 0.04 cm) was as described earlier [1,31]. The 2 M NaOH solution, prepared from BDH grade NaOH was employed as the corrodent for this study. Stock solutions of P. amarus extract were prepared by reuxing 1 g of the dried powder leaves of the plant for 1 h in 100 ml 2 M NaOH solution. The reuxed solution was allowed to stand for 8 h, ltered and used as the stock solution. The ltrate (stock solution) was diluted with the appropriate quantity of 2 M NaOH

* Corresponding author. Address: Department of Chemistry, Federal University of Petroleum Resources, Effurum, Nigeria. Tel.: +234 803 3360 504. E-mail address: abiolaolusegun@yahoo.com (O.K. Abiola). 0010-938X/$ - see front matter 2009 Elsevier Ltd. All rights reserved. doi:10.1016/j.corsci.2009.07.006

O.K. Abiola, J.O.E. Otaigbe / Corrosion Science 51 (2009) 27902793

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to obtain inhibitor test solutions of 5, 8, 10, 12, 15 and 20% v/v concentrations. 2.2. Weight loss determination The procedure for weight loss determination was similar to that reported earlier [1,31]. The pre-weighed aluminum coupons were immersed in 200 ml of 2 M NaOH solutions (in open beakers) without and with different concentrations (520% v/v) of the extract at 30 C for total period of 6 h immersion period. The variation of weight loss was monitored at interval of 1 h progressively for a total of 6 h per coupon at 30 C. The coupons were withdrawn at interval of 1 h immersion period, immersed in concentrated (SG 1.42) nitric acid solution at room temperature, scrubbed with a bristle brush under running water, dried and reweighed. The experimental readings were recorded to the nearest 0.0001 g on a Mettler digital analytical balance. Triplicate experiments were set up for each of the concentration. 3. Results and discussion The material loss as corrosion rate (mm/year) of the aluminum specimens as a function of the extract concentration in 2 M NaOH solution monitored at 30 C is summarized in Table 1. Table 1 show that the corrosion rates decreased with the increase in the concentration of the extract in NaOH solutions. This result showed that P. amarus extract acts as corrosion inhibitor for aluminum in NaOH solution at the studied concentration; signifying the inhibition of aluminum corrosion in NaOH solution. The values of percentage inhibition efciency (%I) and surface coverage (h) were determined for 6 h immersion periods from the corrosion rate (r) using the following equations [32]

from the attacks of the aggressive OH ion from the alkaline solution. There are several types of organic compounds [2328] in P. amarus, viz: alkanoids, avonoids, cyanogenic glycosides, carbohydrates, proteins, sugar, steroids and triterpenoids. In addition, it contains 24% of non-volatile, surface active compounds known as saponins and 17% tannins. Saponins are complex compounds that consist of one or more monosaccharide coupled with non-polar aglycones [29], with molecular weight of more than 500. Tannins are water-soluble compounds, esters of an aliphatic and phenolic acids or oligomers and polymers of polyhydroxyavan-3-ol units with molecular weights between 500 and 3000 [30,31]. Also, the leaves of this plant is a rich source of two lignans known as phyllathin and hypophyllathin [2528]. The molecular structures of phyllathin and hypophyllathin compounds show a heterocyclic organic compound with 6 or 7 oxygen atoms.

ru rp 100 ru h %I=100 %I 87:6w Corrosion rate mm=year DAt

1 2 3

where ru is the corrosion rate in the absence of inhibitor, rp is the corrosion rate in the presence of the inhibitor, w is the weight loss of aluminum (mg), D, the density of the specimen (g cm3), A, the area of specimen(cm2), and t, the immersion time (h). The percentage inhibition efciency values (Table 1) for triplicate specimens were precise to 7% and this indicates good reproducibility. Table 1 show that the inhibition efciencies increase with the increase in extract concentration and reach a maximum value of 76% with 20% v/v of extract. This indicates that the organic compounds of the extract are adsorbed onto the aluminum surface resulting in the blocking of the reaction sites, and protects the Al

The inhibition effect of P. amarus is ascribed to the presence of these organic compounds in the extract. Organic compounds having centers for p-electrons and functional groups such as C@C, C@C, OR, NR2 and/or SR have been reported to inhibit corrosion of metals in alkaline or acid solutions [3337]. The adsorption of these compounds on the aluminum surface reduces the surface area that is available for the attack of the aggressive OH ion from the alkaline solution. As presented in Table 1, there is notable decrease in the value of corrosion rate with increasing extract concentration due to higher degree of surface coverage, h because of enhanced inhibitor adsorption. Similar view has been expressed on the inhibition of aluminum by plant extract in alkaline solution [1]. Values of h were tested graphically for t to different adsorption isotherms. As depicted in Fig. 1, a straight line is obtained when c/h is plotted against c and the linear correlation coefcient of the tted data is good (>0.998). This conrms that the inhibition is due to the adsorption of the active organic compounds onto the metal surface and the adsorption obeys the Langmuirs adsorption isotherm [17] expressed as

Table 1 Corrosion rate, inhibition efciency and surface coverage of Phyllanthus amarus extract on aluminum at 30 C for 6 h immersion period. Concentration (%v/v) 0 5 8 10 12 15 20 Corrosion rate (mm/yr) 943 10 322 8 312 12 289 9 256 7 248 11 229 10 Inhibition efciency (%I) 66 2.4 67 4.5 69 4.1 73 5.0 74 5.2 76 6.8 Surface coverage (h) 0.66 0.67 0.69 0.73 0.74 0.76

c 1 c h K

where c is the inhibitor concentration and K the equilibrium constant for the adsorption/desorption process of the inhibitor molecules on the metal surface. The kinetics of the aluminum corrosion in 2 M NaOH and 2 M NaOH-extract systems was studied at 30 C by tting the corrosion data into different rate laws. Fig. 2 depicts the dependence of Wt as a function of time t. The corrosion data t the rate law for zeroorder reaction as expressed [38,39] in Eq. (5)

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O.K. Abiola, J.O.E. Otaigbe / Corrosion Science 51 (2009) 27902793

R = 0.9981

c/ (% v/v)

20 15 10 5 4 6 8 10 12 14 16 18 20

c (% v/v)
Fig. 1. Langmuir adsorption model on the aluminum surface of Phyllanthus amarus extract in 2 M NaOH solution.

200 180 160

control 10 v/v % 12 v/v % 20 v/v%

R2 = 0.9991 R2 = 0.9996 R2 = 0.9997 R2 = 0.9997

References
[1] O.K. Abiola, J.O.E. Otaigbe, O.J. Kio, Gossipium hirsutum. L extracts as green corrosion inhibitor for aluminum in NaOH solution, Corrosion Science 51 (2009) 18791881. [2] D. Mercier, M.-G. Barths-Labrousse, The role of chelating agents on the corrosion mechanisms of aluminium in alkaline aqueous solutions, Corrosion Science 51 (2009) 339348. [3] K.C. Emeregul, A.A. Aksut, The behavior of aluminum in alkaline media, Corrosion Science 42 (2000) 20512067. [4] J. Zhang, M. Klasky, B.C. Letellier, The aluminum chemistry and corrosion in alkaline solutions, Journal of Nuclear Materials 384 (2009) 175189. [5] A.A. El-Shafei, S.A. Abd El-Maksoud, A.S. Fouda, The role of indole and its derivatives in the pitting corrosion of Al in neutral chloride solution, Corrosion Science 46 (2004) 579590. [6] A.I. Onuchukwu, The inhibition of aluminium corrosion in an alkaline medium II:inuence of hard bases, Materials Chemistry and Physics 24 (1990) 337341. [7] S.-I. Pyun, S.-M. Moon, S.-H. Ahn, S.-S. Kim, Effects of Cl-, NO3- and SO42- ions on alkaline dissolution of pure aluminum in alkaline solution, Corrosion Science 41 (1999) 653667. [8] L. Gnana Sahaya Rosilda, M. Ganesan, M. Anbu Kulandainathan, V. Kapali, Inuence of inhibitors on corrosion and anodic behaviour of different grades of aluminium in alkaline media, Journal of Power Sources 50 (1994) 321329. [9] M. Saleh, A.A. Ismail, A.A. El Hosary, Corrosion inhibition by naturally occurring substances-IX. The effect of the aqueous extracts of some seeds, leaves, fruits and fruit-peels on the corrosion of Al in NaOH, Corrosion Science 23 (1983) 12391241. [10] M. Krishnan, N. Subramanyan, The inuence of some aldehydes on the corrosion and anodic behaviour of aluminium in sodium hydroxide solution, Corrosion Science 17 (1977) 893900. [11] H.B. Shao, J.M. Wang, Z. Zhang, J.Q. Zhang, C.N. Cao, The cooperative effect of calcium ions and tartrate ions on the corrosion inhibition of pure aluminum in alkaline solution, Materials Chemistry and Physics 77 (2002) 305309. [12] I. Sekine, Y. Nakahata, H. Tanabe, The corrosion inhibition of mild steel by ascorbic and folic acids, Corrosion Science 28 (1988) 987. [13] E.E. Oguzie, R.N. Okolue, C.E. Ogukwe, C. Unaegbu, Corrosion inhibition and adsorption behaviour of bismark brown dye on aluminium in sodium hydroxide, Materials Letters 60 (2006) 33763378. [14] Y. Li, P. Zhao, Q. Liang, B. Hou, Berberine as a natural inhibitor for mild steel in 1 M H2SO4, Applied Surface Science 252 (2005) 12451253. [15] A.M. Abdel-Gaber, B.A. Abd-El-Nabey, I.M. Sidahmed, A.M. El-Zayady, M. Saadawy, Inhibition action of some plant extracts on the corrosion of steel in acidic media, Corrosion Science 48 (2006) 27652779. [16] A.M. Abdel-Gaber, B.A. AbdEL-Nabey, M. Saadawy, The role of acid anion on the inhibition of the acidic corrosion of steel by lupine extract, Corrosion Science 51 (2009) 10381042. [17] O.K. Abiola, N.C. Oforka, E.E. Ebenso, N.M. Nwinuka, Eco-friendly corrosion inhibitors; the inhibitive action of Delonix regia extract for the corrosion of aluminium in acidic media, Anti-Corrosion Methods and Materials 54 (2007) 219224. [18] E.E. Oguzie, Corrosion inhibition of aluminium in acidic and alkaline media by Sansevieria trifasciata extract, Corrosion Science 49 (2007) 15271539. [19] A. El-Hosary, R.M. Saleh, A.M. Sharns, El. Dm, Corrosion inhibition by naturally occurring substancesI. The effect of Hibiscus subdariffa (karkade) extract on the dissolution of Al and Zn, Corrosion Science 2 (1972) 897904. [20] P.B. Raja, M.G. Sethuramam. Strychnos nux-vomica an eco-friendly corrosion inhibitor for mild steel in 1 M sulfuric acid medium, Materials and Corrosion 60 (2009) 2228. [21] A.M.A.M. Abdel-Gaber, E. Khamis, H. Abo-ElDahab, Sh. Adeel, Inhibition of aluminium corrosion in alkaline solutions using natural compound, Materials Chemistry and Physics 109 (2008) 297305. [22] J. Mabrour, M. Akssira, M. Azzi, M. Zertoubi, N. Saibi, A. Messaoudi, A. Albizane, S. Tahiri, Effect of vegetal tannin on anodic copper dissolution in chloride solutions, Corrosion Science 46 (2004) 18331847.

W t (mg cm )

-2

140 120 100 80 60 40 20 0 1.5

2.5

3.5

4.5

5.5

6.5

t (Hours)
Fig. 2. Variation of Wt for aluminum coupons in 2 M NaOH solution with and without Phyllanthus amarus extract at 30 C.

W t kt

where Wt is the weight loss of aluminum at time t and k is the zeroorder rate law. The obtained linear plots with good correlation coefcients of >0.998; conrm a zero-order kinetics for the corrosion of aluminum in NaOH solution with and without the extract. The corrosion rate of aluminium in alkaline solution is under anodic control [40,41] which is:
Al 4OH ! AlOH 4 3e

Fig. 2 reects the reaction order with respect to aluminum. This result suggests that the presence of the extract does not inuence the anodic reaction order. The linearity of the curves in the absence and presence of the extract implies that its presence does not change the kinetics of the corrosion reaction though it signicantly reduces its rate as presented in Table 1. 4. Conclusions The alkaline extract of P. amarus inhibits the corrosion of aluminium in 2 M NaOH solutions, with inhibition efciency of 76% at 20% v/v extract concentration and the adsorption of the inhibitor molecules was consistent with Langmuir adsorption isotherm. A zero-order kinetics relationship was obtained from the kinetics treatment of the data of weight loss measurements. Acknowledgements The authors acknowledged Ms A.A. Phillips for assistance in performing some measurements.

O.K. Abiola, J.O.E. Otaigbe / Corrosion Science 51 (2009) 27902793 [23] P.C. Okafor, M.E. Ikpi, I.E. Uwah, E.E. Ebenso, U.J. Ekpe, S.A. Umoren, Inhibitory action of Phyllanthus amarus extracts on the corrosion of mild steel in acidic media, Corrosion Science 50 (2008) 23102317. [24] C.U. Igwe, L.A. Nwaogu, C.O. Ujuwondu, Assessment of the hepatic effects, phytochemical and proximate compositions of Phyllathus amarus, African Journal of Biotechnology 6 (2007) 728731. [25] A.K. Tripathi, R.K. Verma, A.K. Gupta, M.M. Gupta, S.P.S. Khanuja, Quatitative determination of phyllanthin and hypophyllantin in Phyllanthus species by high-performance thin layer chromatography, Phytochemical Analysis 17 (2006) 394397. [26] A. Sharma, R.T. Singh, S.S. Handa, Estimation of phyllanthin and hypophyllathin by high performance liquid chromatography in Phyllathus amarus, Phytochemical Analysis 4 (1993) 226229. [27] S. Deb, S.K. Mandal, TLC-densitometric determination of phyllanthin and hypophyllathin in Phyllathus amarus (Bhumialaki) and polyherbal formulations, Indian Drugs 33 (1996) 415416. [28] C. Mahidol, P. Sahakitpichan, S. Ruchirawat, Bioactive natural products from Thai plants, Pure and Applied Chemistry 66 (1994) 23532356. [29] J.-P. Vincken, L. Heng, A. Groot, H. Gruppen, Saponins, classication and occurrence in the plant kingdom, Phytochemistry 68 (2007) 275297. [30] T. Umezawa, Chemistry of extractives, in: D.N.-S. Hon, N. Shiraishi (Eds.), Wood and Cellulosic Chemistry, Marcel Dekker, New York, 2001, pp. 213241. [31] S. Martinez, I. Stern, Thermodynamic characterization of metal dissolution and inhibitor adsorption processes in the low carbon steel/mimosa tannin/sulfuric acid system, Applied Surface Science 199 (2002) 8389. [32] O.K. Abiola, Adsorption of 3-(4-amino-2-methyl-5-pyrimidyl methyl thiazolium chloride on mild steel, Corrosion Science 48 (2006) 30783090.

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[33] E.H. EI Ashry, A. EI Nemr, S.A. Essawy, S. Ragub, Corrosion inhibitors part V: QSAR of benzimidazole and 2-substituted derivatives as corrosion inhibitors by using the quantum chemical parameters, Progress in Organic Coatings 61 (2008) 1120. [34] O.K. Abiola, Studies on the inhibition of aluminium alloy (3SR) corrosion by (4amino-2-methyl-5-pyrimidinyl methylthio) acetic acid and its precursor in hydrochloric acid (HCl) solution, Corrosion and Materials 10 (2007) 1015. [35] K.C. Emregul, M. Hayvali, Studies on the effect of vanillin and protocatechualdehyde on the corrosion of steel in hydrochloric acid, Materials Chemistry and Physics 83 (2004) 209216. [36] S. Vishwanatham, N. Haldar, Furfuryl alcohol as corrosion inhibitor for N80 steel in hydrochloric acid. Corrosion Science 50 (2008) 2999 3004. [37] S.V. Ramesh, A.V. Adhikari, N-[4-(diethylamino)benzylidine]-3-{[8-(triuoromethyl) quinolin-4-yl] thio} propane hydrazide) as an effective inhibitor of mild steel corrosion in acid media, Materials Chemistry and Physics 115 (2009) 618627. [38] S.S. Zumdahl, Chemical Principles, fourth ed., Houghton Miflin Company, Boston, 2002. [39] T. Engel, P. Reid, Physical Chemistry, rst ed., Pearson Education, New Delhi, 2006. [40] A. Mukherjee, I.N. Basumallick, Complex behaviour of aluminium dissolution in alkaline aqueous 2-propanol solution, Journal of Power Sources 58 (1996) 183187. [41] R.D. Armstrong, V.J. Braham, The mechanism of aluminium corrosion in alkaline solutions, Corrosion Science 38 (1996) 14631471.