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International Journal of Chemical Science and Technology
Universal Research Publications. All rights reserved

ISSN 2249-8532
Original Article
Corrosion Inhibition study of IS: 2062 Grade-A Low carbon steel in 1M HCl by L-
Tryptophan – Weight Loss, ICP-OES and SEM-EDX studies
TÜV Rheinland (India) Pvt.Ltd, 17B, Electronic City Phase 2, Hosur road, Bangalore-560100, India
Department of Chemistry, B.N.M.Institute of Technology, BSK 2 nd Stage, Bangalore 560 070, India
P.G and Research Department of Chemistry, A.V.V.M. Sri Pushpam College, Poondi-613 503, India
Received 22 May 2013; accepted 03 June 2013
The corrosion inhibition characteristics of amino acid L-tryptophan on IS: 2062 grade-A low carbon steel in 1M HCl
solution at 300C temperature was studied by using weight loss, Inductively Coupled Plasma Optical Emission
Spectrophotometer (ICP-OES) and Scanning Electron Microscope with Energy Dispersive X- Ray analyzer (SEM-EDX)
techniques. Measurements were conducted without and with various concentrations of L-tryptophan and the inhibition
efficiency (IE %) has been studied accordingly. The highest Inhibition Efficiency (IE %) of 89.74% was observed in the
presence of L-tryptophan concentration of 10-1 moles at 300C. These measurements were complemented with ICP-OES
examinations of the electrolyte solution, SEM and EDX characterization of the electrode surface. The addition of very
small concentration (1mM) of potassium iodide as synergizing agent on the corrosion inhibition behavior of L-tryptophan
was also studied. The inhibition efficiency (IE) of L-tryptophan was not significantly altered by KI.
© 2013 Universal Research Publications. All rights reserved
Key words : Inhibition L-Tryptophan Low carbon steel Green Inhibitor HCl Medium ICP-OES.
1) INTRODUCTION: the metal surface, thus blocking the active corrosion sites.
According to recent estimate the loss due to corrosion is The corrosion inhibitors are generally used to protect
USD 4.0 Billion (INR 20000 crores). Some earlier metals against the attack of the acid solutions, which are
research indicates that every 90 seconds one tonne of steel widely used in acid pickling, industrial cleaning, acid
is converted completely into rust [1, 2]. The cost of descaling, oil-well acidizing, etc. However, most of the
corrosion has been reported from many studies to be in the commercially available inhibitors are synthetic chemicals,
order of 1–5% of GNP for any country [1, 3]. Corrosion expensive and hazardous (CMR Cat 1&2) to both human
cannot be stopped but its severity can be controlled. beings and the environments, and need to be replaced by
Corrosion inhibitors are of great practical importance, non toxic and environmental friendly green organic
being extensively employed in minimizing metallic waste compounds. In recent years, number of eco-friendly
in engineering materials [4]. Since low carbon steel is one compounds such as extract of common plants which
of the best preferred materials for construction applications contain many organic compounds, e.g., amino acids,
due its easy availability and its excellent properties alkaloids, fatty acids, carbohydrates, tannins and pigments,
including ductility and toughness. But its use restricted in have been exploited as green alternative to toxic and
acidic environments because of its susceptibility towards hazardous compounds [9]. This proved to be an efficient
corrosion. The use of inhibitors is one of the best-known and inexpensive method of corrosion protection of metals.
methods of corrosion protection. The addition of The amino acid which contains carboxyl and amino
heterocyclic organic compounds containing nitrogen, sulfur functionalities bonded to the same carbon atom are non-
and oxygen have been widely used as potential corrosion toxic, relatively cheap and easy to produce in purities
inhibitors in acid solutions [5-8] is one of the most greater than 99%. It has been shown by various authors that
practical and well proven methods of achieving this. These some amino acids can act as corrosion inhibitors, which has
compounds prevent corrosion either by getting adsorbed, or generated an increasing interest in these compounds as
by forming a protective layer or an insoluble complex on substitutes to conventional corrosion inhibitors that are

International Journal of Chemical Science and Technology 2013; 3(2): 47-53

usually toxic [10-14]. Inductively Coupled determined based on the position of the photon rays. and has been reported in the literature [5. dimension of 4. The chemical method of corrosion rates finally washed and degreased using acetone.05 % P. and International Journal of Chemical Science and Technology 2013. This makes the ICP-OES weighed by electronic digital analytical balance (Make: instrument is superior in the trace and environmental Essae Teroka. resulted in improved inhibition efficiency of many organic 3) METHODS compounds.4 cm (T) were which makes the corrosion rate obtained only a long-term used for weight loss measurements. scales or rust. The photon wavelength are measured. The element measurement capability (72 elements in a single concentration of L-tryptophan was kept in the range of 10-5 scan). Hence few details about the corrosion process traces of impurities.40 % Si and 0. The present work was undertaken to optical emission spectrometry. measurements involved determination of the dissolved To hold the specimens a hole of 1. high stability. When the excited atoms return effect of the addition of very small concentration (1mM) of to low energy position. data performed after an exposure of 1 h. such sophisticated instrument efficiency (%IE) was calculated by using the following provides an excellent continuous chemical monitoring and equation: robust analytical method for corrosion rate. When plasma energy is investigate the corrosion inhibition behavior of L. The corrosion inhibition of Fe in 1M Plasma Optical Emission Spectrophotometer (ICP-OES) HCl using twenty two different common amino acids and and Scanning Electron Microscope with Energy Dispersive four related compounds has been investigated by using X. However.0 cm (W) × 0. T is the time in hour and Scanning Electron Microscope was applied to confirm that K is constant with a value of 8. polished with Silicon carbide emery papers of grade 1/0. Range : 1mg to 220mg) with four decimal analysis in aqueous and organic media in complex samples. The advantages out at 300C in 1 M HCl. and dried up.8 cm (L) × 1.8 cm (L) × 1. with any other test. it is time consuming. ICP-OES is one method of method by using EDX. % = (1.53 % Mn. The elements (atoms) is excited. optimum selectivity and superior to 10-1 M in 1M HCl. The chemical method of corrosion inhibition efficiency Bare (without inhibitor) and L. A is the area of exposure in cm2.23 % C. In this section. emission rays (spectrum rays) are potassium iodide as synergizing agent on the corrosion released and the emission rays that correspond to the inhibition behavior of L-tryptophan was also studied. 2) MATERIALS amino acids with longer hydrocarbon chains showed In the present work. D is the density in g/cc. with a L-tryptophan is a derivative of indole.5 M H2SO4 in the (Merck) of analytical grade with 99. To remove the last average. given to a sample solution from outside. (ICP-OES) Inhibition Efficiency. the component tryptophan on low carbon steel in 1M HCl solution. corresponding corrosion data obtained from them approach Corrosion rate (mmpy) = (K x W) / D x A x T service conditions more accurately than the data obtained Where W s the weight loss in mg. and balance Fe. 3/0 and 4/0 followed with a velvet cloth polishing in an HCl were determined by a chemical method other than alumina medium.1) Weight loss measurements At present. weight loss measurement is the mostly This is the simplest and most widely used method for employed method to acquire the corrosion rate data for evaluating corrosion rated and the component materials.Ray analyzer (SEM-EDX) potentiodynamic polarization curves [15].4 cm (T) were structure of the compound suggests that it has strong used for corrosion Inhibition studies.76 x 10-6 mmpy the self-assembled films on the low carbon steel surface 3. The element type is techniques used are weight loss.17] 3.0 cm (W) × 0.05 % S. The SEM spectroscopy (ICP-OES) method. The composition protective film formed on low Plasma optical emission spectrometry. Additional groups which increased specimens equivalent to IS: 2062 Grade A specification electron density on alpha amino group also increased the having composition (weight %): 0. Other chemicals and reagents Moretti and Guidi [16] reported the corrosion inhibition of such as hydrochloric acid and potassium iodide were L-tryptophan on copper in aerated 0. experimental corrosion rates for low carbon steel in 1M 2/0.tryptophan modified low measurements are involved in determination of the carbon steel sheets after exposed for 1 h in 1M HCl dissolved cation using ICP-OES (Inductively Coupled solutions. Make: Perkin Elmer carbon steel surface was analyzed in a non. accuracy before and after exposure. The polished specimen with mirror finish weight loss.9% purity. commercial grade low carbon steel greater inhibition. so that the steel in the presence and absence of inhibitor respectively. micrographs with surface morphologies of the as polished. grade 35% HCl using double distilled water.destructive Model Optima 7000DV). (Merck) was used as such. The molecular dimension of 4. In general.2) Inductively coupled plasma optical emission can protect the metal from corrosion. the specimens were during the experimental period are revealed.w1/w2) x 100 provides therefore the most reliable results concerning the Where w1 & w2 are the weight losses (mg) for low carbon efficiency of a given inhibitor compound. 3(2): 47-53 48 . The addition of halide ions solutions of HCl were prepared using double distilled to organic compounds has shown synergistic effect and water. metal coupons at natural environmental corrosion test The specimens were cut into rectangular shape with a stations in many countries. The weight loss experiments were dynamic range for concentration as well as calculation. The nitrogen containing amino acid 0. The weight loss studies were carried emission spectrometry) method of analysis.7 mm diameter was cation using ICP-OES (inductively coupled plasma optical made near the edge. The inhibition In the corrosion studies. 0. 1. The specimens were reporting and data reprocessing. L-Tryptophan potential to become an effective corrosion inhibitor. inhibition efficiency. The stock temperature range of 20-500 C. The test solution was made of AR offered by ICP-OES method of analysis includes a multi.

Samples for SEM experiments 4) RESULTS AND DISCUSSION: were used steel sheets of dimension of 4. at 300C.264 1. International Journal of Chemical Science and Technology 2013.E1 = E. corrosion rate and IE at different concentrations of L- modified steel sheet after corrosion in 1M HCl for 1 h. Table-I : Effect of concentration of L.8 cm (L) × 1. cm s (T) . (Fig.Planck’s constant 6. morphological and compositional and minor element analysis.wavelength of light.6386 18. The maximum increase in IE of 89.6068 16.5 wt%. [HCl] : 1M Inhibition Efficiency.1641 16.0453 46. but is in resolution.tryptophan loss.Tryptophan on IS: 2062 Grade-A Low carbon steel in 1M HCl Inhibitor: L- Tryptophan.22 4.58 1.05 10. Energy Dispersive X-ray Where. E2 .13 4. Exposure time : 1 hr. which measures intensity.7352 0. The high.626068 × Spectroscopy (EDS.tryptophan Scanning Electron Microscope was used for elemental [5]. This hc information is sent to a pulse processor.84 18.08 10.2). provide information on the chemical composition of a 3. but lacks trace-element information make them very useful in a variety of science analysis.16 4.74 % was observed analysis or chemical characterization of the film formed on at a concentration of 10-1M at 300C. a detector that IE increases with increase in concentration. The polishing procedure was the same as The corrosion of low carbon steel 1M HCl in the absence that mentioned above. Temp : 30 0C. c-Velocity of light 3 x 108 meters per quantitative X-ray microanalytical technique that can second. technique.20 3 102 44.27 4.4) Energy dispersive X-ray analysis (EDX) clearly seen that the corrosion rate of low carbon steel EDX from Oxford Instruments with INCA 250 Energy depends upon inhibitor concentration.1) Weight loss measurements: (W) × 0.0820 2. Corrosion Sl. and industrial applications.00 1. SEM is a powerful magnification tool that utilizes focused The detection limit of EDX analysis in the SEM depends beams of electrons to obtain information.17 10. The corrosion rates Microanalysis System attached with Carl Zeiss EVO 18 are significantly reduced in the presence of L.7206 0. which was not further steel surface.6408 18.5683 0.8191 16.0cm 4. So that. reveal electromagnetic radiation and the matter.the content of each element is determined based on the rays' was used to convert X-ray energy into voltage signals.E % M (L). h . and the presence of different concentrations of amino acid Scanning Electron Microscope EVO 18 from Carl Zeiss L-tryptophan was studied at 300 C using weight loss was used to observe the morphology of the steel sheets.77 16.No (W). w1= Weight loss with inhibitor. (Fig.0839 2 101 45.81 The plots of corrosion rate as a function of L-tryptophan concentration.97 1. The immersion time was 1 h.62 5 104 49. I.try] Length Thicknes Weight Loss. on the composition of the sample being analyzed.38 4. It is an effective technique for major provide topographical.78 18. reveal that corrosion rate decreases with increase in concentration.4 cm.0725 13. it is 3. as E  h  the signals and passed them into an analyzer for data  display and analysis.1-0.46 4.w1 / w2 ) x 100. Table . The plots of IE investigation of sample through interaction between as a function of L-tryptophan concentration. λ . tryptophan at 300 C temperatures.0663 20. cm W = (A-B) g Rate 10-8 cm (A) g g 1 0 44.72 16.8329 0.09 4 103 45.74 0.5982 0.3) Scanning Electron Microscope examinations (SEM) sample for elements with atomic number (Z) >3.E% = ( 1. EDX or XEDS) is a qualitative and 10-34 m2 kg / s. at 300C.1188 0.65 15.8992 15. As a type of spectroscopy.44 10.1). 3(2): 47-53 49 .57 16. three-dimensional images produced by SEM to the range 0.0086 89.I shows the calculated values of weight including the bare steel sheet and the L. weight (B) I.91 10. w1= Weight loss with inhibitor Width Initial Final weight [L.91 10. From these data. it relies on the affected by adding KI as synergizing agent.58 6 105 49.

3 ICP-OES Calibration curves for Iron and Manganese content analysis Fig. thus the surface data reprocessing.5 2 101 291. method for corrosion rate.0 M HCl solutions without and with various concentrations of L. while the L-tryptophan–modified steel sheet was details of the as polished.4. In the corrosion concentration. The advantages offered follows from the data of Table II that the corrosion rate is by ICP-OES method of analysis includes a multi-element suppressed and the corrosion inhibition strengthened with measurement capability (72 elements in a single scan). weight loss measurement is the mostly the most reliable results concerning the efficiency of a employed method to acquire the corrosion rate data for given inhibitor compound. Exposure time: 1 hr. 3 (a) ICP-OES Calibration curves for Fe Fig. Temp: 30 0C. This trend may result stability. The open-circuit free corrosion rate was average. Table-II: Dissolved Fe content in 1.Tryptophan. The calibration curves for Iron and The chemical method of corrosion rates measurements Manganese content were shown in Fig.78 4 103 2364. The SEM micrographs with surface morphology damaged. However. The on the iron surface which can protect the metal from surface of the bare low carbon sheet was completely corrosion. Hence few details about the corrosion process determined here separately by determination of dissolved during the experimental period are revealed. M Fe concentration in mg/L Corrosion Rate 10 4 1 0 2786. The L- superior in the trace and environmental analysis in aqueous tryptophan concentration was plotted against iron (Fe) and organic media in complex samples. This means the presence of L- tryptophan modified low carbon steel sheets after corrosion tryptophan films can effectively protect steel surface from for 1 hour in 1M HCl solutions are shown in Fig. data reporting and with the increase in inhibitor concentration. These make the ICP-OES instrument is is efficiently separated from the medium [18-21].5 6.Tryptophan . using the (ICP-OES) technique Inhibitor: L. not so severely damaged. Fe ions in 1.3 (b) ICP-OES Calibration curves for Mn 4. such sophisticated instrument provides an excellent identified. (ICP-OES) provides therefore At present.2) Inductively Coupled Plasma Optical emission continuous chemical monitoring and robust analytical spectroscopy (ICP-OES) method. of the solution containing dissolved Fe ions were OES (inductively coupled plasma optical emission withdrawn and total dissolved iron were analyzed.75 51. using the (ICP- determined by a chemical method other than weight loss. The critical inhibitor concentration was studies.2 51. 3(2): 47-53 50 . high increase in inhibitor concentration. conditions more accurately than the data obtained with any which makes the corrosion rate obtained only a long-term other test [18]. so that the corresponding metal coupons at natural environmental corrosion test corrosion data obtained from them approach service stations in many countries. bare (without inhibitor) and L.3) SEM Analysis: the six SEM microphotographs.48 Fig. it is time consuming. It spectrometry) method of analysis. Known aliquots involved determination of the dissolved cation using ICP. 4 (a-f).0 M HCl solutions without and with various experimental corrosion rates for iron in HCl were concentrations of L. [HCl]: 1M Sl. OES) technique. The bare one had suffered SEM was applied to confirm that the self-assembled films more severe corrosion than inhibitor protected one. SEM photographs obtained from low can be observed that there are distinct differences between carbon steel surface after the specimens immersed in 1M International Journal of Chemical Science and Technology 2013.trptophan at 300C. optimum selectivity and superior dynamic range from the fact that adsorption and surface coverage increases for concentration as well as calculation. 3.78 5 104 2621.35 3 102 2250 48. In this section.No L.Tryptophan at 300C. It corrosion [22].

tryptophan the covered the electrode surface. 5 (b) showed that in strongly damaged in the absence of the inhibitor.4) Energy dispersive X-ray analysis (EDX) indicated by the Fe and O signals. Fig. the O signal is significantly enhanced due to HCl solution without inhibitor molecules (blank) was failed the oxygen atoms of the head group. 4 (a-f) SEM Micrographs of Low carbon steel surface HCl for 1h in the absence and the presence of 10 -4 to 10-1M strong protective film of the inhibitor molecules on the of L-tryptophan were shown in Fig. it surface of low carbon steel sample. oxygen due to the inhibitor. Fig. it revealed that there was a good the electrode surface. These data show that a because it is severely weakened by external corrosion as carbonaceous material containing oxygen atoms has shown in Fig. 5 (a). spectrum in case of carbon steel sample immersed in 1M In addition. 5 (a) shows a good surface properties. uninhibited HCl solutions. The action of inhibitor could be seen that in presence of the inhibitor. The formation of such a barrier film protective film adsorbed on specimens surface. while the existence of C (due to the carbon atoms of L. Fig. which was is confirmed by SEM and EDX examinations of the responsible for the inhibition of corrosion. 3(2): 47-53 51 . 4 (b) that the specimen surface was survey spectra presented in Fig. as a representative example). in inhibited The composition of protective film formed on low carbon HCl solutions (in presence of various concentrations of L- steel surface was analyzed using EDX as shown in Fig. By adding 10-1 M of L. as 4. It could be electrode surface.5(c-f) the (a-f). 5 (c & d). because the carbon signal and all the and nitrogen band was observed due to the formation of a previous results plead on the favour that the corrosion International Journal of Chemical Science and Technology 2013. Fig. The EDX spectrum of polished carbon steel sample EDX spectra showed an additional line characteristic of the in Fig..Tryptophan). The EDX observed from Fig. This layer is undoubtedly decrease of iron band and appearance of carbon. However. the rate of is related to adsorption and formation of a barrier film on corrosion was suppressed. 4 (c & d). iron oxide is present. 5 tryptophan. 4 (c-f) respectively.

[23] as adsorption onto the electrode surface blocking the confirmed from SEM and EDX examinations Fig 4 and 5.tryptophan suggests that adsorption may occur film produced on the steel surface. The molecular structure carbon steel surface. International Journal of Chemical Science and Technology 2013. Fig. This film retarded the reduction of coordinate bonds between the lone electron pairs of the dissolution of iron in carbon steel surface oxygen atoms and the empty orbitals of iron atoms which References: enhance the attraction between the L. Alam Khan. Mobin. which was not presence of a transition metal. 5 (a-f) EDX graphs of low carbon steel surface inhibition effect of the L. blocks access to the active site of corrosion on interaction: physical adsorption and chemisorption. This is possible in case of a the maximum increase in Inhibition Efficiency of 89. reducing the aggressiveness of attack at these general. M. Corrosion Science 52(2010) 1762-1770. having vacant.74 positive as well as a negative charge of the surface. electron orbitals and of an inhibitor with molecules having 2) ICP-OES measurements. the proceeding of physical adsorption requires the sites. The main conclusions of the present study could be Chemisorption process involves charge sharing or charge. reconfirms that the increase in relatively loosely bound electrons or heteroatom with a inhibitor concentration reduces the corrosion rate of low lone pair of electrons is necessary. 3(2): 47-53 52 . The chemisorbed L. through two lone pairs of electrons on the oxygen atoms of 3) SEM and EDX observations of the electrode surface the hydrophilic head group. This is mainly due to protective of the L.Tryptophan 1.tryptophan is due to their Tryptophan molecules form a protective layer. The % at a concentration of 10-1M at 300C. M. low-energy further affected by adding KI as synergizing agent. It is well known that the adsorption of covering the entire surface quickly. This type of adsorption is showed that a film of inhibitor molecules is formed on expected to be chemical due to the possible formation of the electrode surface. CONCLUSION and charged species in the bulk of the solution. Mosarrat Parveen. and possibly at the organic compounds can be described by two main types of same time. presence of both electrically charged surface of the metal 5. summarized in the following points: transfer from the inhibitor molecules to the metal surface to 1) In weight loss measurements L-tryptophan has shown form a coordinate type of bond. In the surface. corrosion process. molecules and electrode surface.

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