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Materials Letters 62 (2008) 113 116 www.elsevier.com/locate/matlet

Natural products as corrosion inhibitor for metals in corrosive media A review

Pandian Bothi Raja, Mathur Gopalakrishnan Sethuraman
Department of Chemistry, Gandhigram Rural Institute Deemed University, Gandhigram-624 302, Tamil Nadu, India Received 11 January 2007; accepted 23 April 2007 Available online 4 May 2007

Abstract The use of inhibitors for the control of corrosion of metals and alloys which are in contact with aggressive environment is an accepted practice. Large numbers of organic compounds were studied and are being studied to investigate their corrosion inhibition potential. All these studies reveal that organic compounds especially those with N, S and O showed significant inhibition efficiency. But, unfortunately most of these compounds are not only expensive but also toxic to living beings. It is needless to point out the importance of cheap, safe inhibitors of corrosion. Plant extracts have become important as an environmentally acceptable, readily available and renewable source for wide range of inhibitors. They are the rich sources of ingredients which have very high inhibition efficiency. This article gives a vivid account of natural products which are used as corrosion inhibitors for various metal and alloys in aggressive media. 2007 Elsevier B.V. All rights reserved.
Keywords: Metals; Corrosion inhibitors; Natural products; Toxicity; Green inhibitors

1. Introduction Pure metals and alloys react chemically/electrochemically with corrosive medium to form a stable compound, in which the loss of metal occurs. The compound so formed is called corrosion product and metal surface becomes corroded. Corrosion involves the movement of metal ions into the solution at active areas (anode), passage of electrons from the metal to an acceptor at less active areas (cathode), an ionic current in the solution and an electronic current in the metal. The cathodic process requires the presence of an electron acceptor such as oxygen or oxidising agents or hydrogen ions [16]. Corrosion can be minimized by suitable strategies which in turn stifle, retard or completely stop the anodic or cathodic reactions or both. Among the several methods of corrosion control and prevention, the use of corrosion inhibitors [712] is very popular. Corrosion inhibitors are substances which when added in small concentrations to corrosive media decrease or prevent the reaction of the metal with the media. Inhibitors are added to many systems viz., cooling systems, refinery units, chemicals,
Corresponding author. Tel.: +91 451 2452371. E-mail address: mgsethu@rediffmail.com (M.G. Sethuraman). 0167-577X/$ - see front matter 2007 Elsevier B.V. All rights reserved. doi:10.1016/j.matlet.2007.04.079

oil and gas production units, boiler etc. Inhibitors function by adsorption of ions or molecules onto metal surface. They reduce the corrosion rate by, Increasing or decreasing the anodic and/or cathodic reaction Decreasing the diffusion rate for reactants to the surface of the metal Decreasing the electrical resistance of the metal surface Inhibitors are often easy to apply and offer the advantage of in-situ application without causing any significant disruption to the process. However, there are several considerations when choosing an inhibitor: Cost of the inhibitor can be sometimes very high when the material involved is expensive or when the amount needed is huge. Toxicity of the inhibitor can cause jeopardizing effects on human beings, and other living species. Availability of the inhibitor will determine the selection of it and if the availability is low, the inhibitor becomes often expensive. Environment friendliness.

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Sanyal [13] in his review has given a vivid account of organic corrosion inhibitors including the classification and mechanism of action. He has attributed the corrosion inhibition potential to the donation of lone pair of electron to metal atoms. A number of heterocyclic compounds [1417] have been reported as corrosion inhibitors and the screening of synthetic heterocyclic compounds is still being continued. Though many synthetic compounds showed good anticorrosive activity, most of them are highly toxic to both human beings and environment. The safety and environmental issues of corrosion inhibitors arisen in industries has always been a global concern. These inhibitors may cause reversible (temporary) or irreversible (permanent) damage to organ system viz., kidneys or liver, or to disturb a biochemical process or to disturb an enzyme system at some site in the body. The toxicity may manifest either during the synthesis of the compound or during its applications. These toxic effects have led to the use of natural products as anticorrosion agents which are eco-friendly and harmless. In recent days many alternative eco-friendly corrosion inhibitors have been developed, they range from rare earth elements [18 20] to organic compounds [2124]. In the present review a detailed account of green inhibitors is given. 2. Natural corrosion inhibitors In 1930, plant extracts (dried stems, leaves and seeds) of Celandine (Chelidonium majus) and other plants were used in H2SO4 pickling baths. An additive, ZH-1 consisting of finely divided oil cake, a by product formed in the phytin manufacture was developed for the control of corrosion. Animal proteins (by products of meat and milk industries) were also used for retarding acid corrosion. The additives used in acid, included flour, bran, yeast, a mixture of molasses and vegetable oil, starch and hydrocarbons (tars and oils). Antra made by sulphonating anthracene or anthracene oil and TM consisting of heavy oils obtained in the fractionation of coal tar were used in Russia [13]. Saleh et al. [25] reported that Opuntia extract, Aleo eru leaves, orange and mango peels give adequate protection to steel in 5% and 10% HCl at 25 and 40 C. Srivatsava [26] found that tobacco, black pepper, caster oil seeds, acacia gum and lignin can be good inhibitors for steel in acid medium. In fact, the first patented corrosion inhibitors used were either natural product such as flour, yeast etc., [27] or by products of food industries for restraining iron corrosion in acid media [28]. Cabrera et al. found that molasses treated in alkali solution inhibit the corrosion of steel in HCl used in acid cleaning [29]. Srivatsava and Sanyal studied the performance of caffeine [30] and nicotine [31] in the inhibition of steel corrosion in neutral media. Khamis et al. [32] has proved the use of herbs (such as coriander, hibiscus, anis, black cumin and garden cress) as new type of green inhibitors for acidic corrosion of steel. El-Etre [33] has studied the application of natural honey as corrosion inhibitor for copper in aqueous solution. Similar study has also been conducted on carbon steel [34]. Parikh et al. [35] studied the anticorrosion activity of onion, garlic and bitter gourd for mild steel in HCl media.

Ethanolic extract of Ricimus communis leaves was studied for the corrosion inhibition of mild steel in acid media by Sathyanathan et al. [36]. Aqueous extract of Hisbiscus flower and Agaricus has been studied as corrosion inhibitors for industrial cooling system by Minhaj et al. [37]. The application of extracts of henna, thyme, bgugaine and inriine was investigated for their anticorrosion activity [3841]. The effect of addition of bgugaine on steel corrosion in HCl is patented [42]. Saleh et al. studied the peel of pomegranate [43] and Beet root [44] as corrosion inhibitor for mild steel in acid media. Sanghvi et al. have investigated the anticorrosion activity of Embilica officianilis, Terminalia chebula, Terminalia belivia [45], Sapindus trifolianus and Accacia conicianna [46]. Corrosion inhibition has also been studied for the extracts of Swertia angustifolia [47], Eucalyptus leaves [48], Eugenia jambolans [49], Pongamia glabra, Annona squamosa [50], Accacia Arabica [51], Carica papaya [52], Azadirachta indica [53] and Vernonia amydalina [54] for steel in acid media. The anticorrosion effect of Andrographis paniculata [55] and tea wastes [56] have been reported from our laboratories. Kliskic et al. analyzed aqueous extract of Rosmarinus officinalis [57] as corrosion inhibitor for Aluminium alloy corrosion in chloride solution. Guar gum was analyzed for its anticorrosion activity by Abdallah et al. [58]. Martinez and Stern have studied the inhibitory mechanism of low carbon steel corrosion of Mimosa tannin in H2SO4 media [59]. Oguzie investigated the efficiency of Telforia occidentalis extract as corrosion inhibitor in both HCl and H2SO4 media [60]. The extracts of Chamomile, Halfabar, Black cumin and kidney bean were analyzed for their inhibitive action of corrosion of steel in acid media by Abdel-Gaber et al. [61]. El-Hosary et al. [62] studied the corrosion inhibition of Aluminium and Zinc in HCl using Hisbiscus subdariffa extract. Avwiri and coworkers studied the inhibitive action of Vernonia amygdalina on the corrosion of Aluminium alloys in HCl and HNO3 [63]. The inhibition effect of Zenthoxylum alatum extract on the corrosion of mild steel in aqueous orthophosphonic acid was investigated by Gunasekaran et al. [64]. Nypa fructicans wurmb [65] leaves were studied for the corrosion inhibition of mild steel in HCl media. Muller [66] investigated the effect of saccharides [reducing sugars fructose and mannose] on the corrosion of Aluminium and Zinc in alkaline media. Hammouti et al. studied the extracts of Ginger [67], jojoba oil [68], eugenol, acetyl-eugenol [69], artemisia oil [70,71] and Mentha pulegium [72] for corrosion inhibition of steel in acid media. Oguzie studied the inhibitive effect of Occium viridis extract [73] on the acid corrosion of mild steel and Sansevieria trifasciata extract [74] on the acid and alkaline corrosion of Aluminium alloy. El-Etre et al. investigated Khillah extract [75] for the corrosion inhibition of SX 316 steel in acid media, Lawsonia extract [76] was studied for effect against acid induced corrosion of metals, Opuntia extract [77] was investigated for the corrosion of Aluminium in acid medium and vanillin [78] for the corrosion of mild steel in acid media. Berberine an alkaloid isolated from Captis was studied for its

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anticorrosion effect for mild steel corrosion in H2SO4 medium [79] by Yan Li et al. Fabrizio Zucchi and Ibrahim Hashi Omar [80] have found that Papaia, Poinciana pulcherrima, Cassia occidentalis and Datura stramonmium seeds, Calotropis procera, Azydracta indica and Auforpio turkiale sap are useful as acid corrosion inhibitors. Sethuraman et al. [81] have studied the acid extract of Datura metel as corrosion inhibitor for mild steel in acid medium. Quinine [82] has been studied for its anticorrosive effect of carbon steel in 1 M HCl by Mohamed Ismail Awad. Anthony et al. has studied the effect of caffeine against chloride corrosion of carbon steel [83]. The corrosion inhibition activity in many of these plant extracts could be due to the presence of heterocyclic constituents like alkaloids, flavonoids etc., Even the presence of tannins, cellulose and polycyclic compounds normally enhances the film formation over the metal surface, thus aiding corrosion. 3. Conclusion The recent trend of reporting the plant extracts as corrosion inhibitors has one main drawback. Rarely the phytochemical investigation is carried out on the extract and efforts are seldom made to pinpoint the active ingredient present in the plant extract. It is also likely that a mixture of constituents present may potentiate the inhibitive effect of one particular constituent. But it is still amazing to see reports wherein inhibition to the extent of 98% efficiency is achieved. It is certain that natural compounds emerge out as effective inhibitors of corrosion in the coming years due to their biodegradability, easy availability and non-toxic nature. Careful perusal of the literature clearly reveals that the era of green inhibitors has already begun. References
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