Accepted Manuscript

Title: Corrosion inhibition of steel in 3.5% NaCl by rice straw

extract

Authors: N.Kamil Othman, S. Yahya, M.Che Ismail

PII: S1226-086X(18)31233-4
DOI: https://doi.org/10.1016/j.jiec.2018.10.030
Reference: JIEC 4228

To appear in:

Received date: 21 February 2018

Revised date: 22 May 2018
Accepted date: 29 October 2018

Please cite this article as: N.Kamil Othman, S.Yahya, M.Che Ismail, Corrosion
inhibition of steel in 3.5% NaCl by rice straw extract, Journal of Industrial and
Engineering Chemistry https://doi.org/10.1016/j.jiec.2018.10.030

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Corrosion inhibition of steel in 3.5% NaCl by rice
straw extract

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N. Kamil Othman a, S. Yahya* a,b , M. Che Ismail b

a
School of Applied Physics, Faculty of Science and Technology, Universiti Kebangsaan

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Malaysia, 43600 UKM Bangi, Selangor, Malaysia.

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b
Department of Mechanical Engineering, Centre for Corrosion Research, Universiti Teknologi

PETRONAS, 32610 Seri Iskandar, Perak, Malaysia.

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Graphical abstract
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ABSTRACT

Inhibition of steel corrosion in 3.5% sodium chloride (NaCl) by rice straw extract (RSE) was

studied via weight loss method up to 42 days immersion. The corrosion inhibition efficiency (IE)

showed a consistent value with the highest IE of 92% and low corrosion rate, 0.013 mm/y. RSE

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was able to reduce pitting corrosion by presenting small hysteresis loop via cyclic polarization

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measurement. The formation of ferric-RSE layer due to complexation was confirmed via surface

analysis. The presence of corrosion products on steel was significantly reduced by immersion in

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RSE. The inhibitory mechanism was proposed to be achieved through interphase inhibition.

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KEYWORDS: Corrosion inhibitor, plant extract, steel, weight loss, interphase inhibition
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INTRODUCTION
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The addition of any chemical into a corrosive environment signifying the role of corrosion
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inhibitors whenever corrosion is inhibited. The interaction of corrosion products in the inhibitor
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system also collaborated to the corrosion inhibition, especially in near neutral solution. This

phenomenon arose when the environment in inhibition systems was chemically changed.
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Corrosion behavior of low-carbon steel in natural and synthetic seawaters has been investigated

by Moller et al., and they found that a different behavior of corrosion was depended on the duration
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of immersion [1]. Kassim and Afidah claimed that there may be a different inhibition mechanism

of adsorption of the organic inhibitor at the oxide-covered metal surface after the displacement of

pre-adsorbed water molecules. The presence of inhibitors has restricted the oxygen diffusion due

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to poor electronic- conductive properties of the thick surface layers [2]. Lorenze and Mansfeld

revealed that the inhibition of steel in chloride near neutral media involved the formation of a

geometry layer and such layer behave interphase coordination on the metal surface [3].

Since organic inhibitors were more preferable in industrial usage, thus there is abundant

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studies of the organic compound have been reported in mitigating the corrosion attack. The use of

polymer compound in formulating corrosion inhibitor also capable to give high inhibition

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efficiency compared to monomer compound. Nowadays, researchers are actively searching for the

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natural sources of polymer with low cost such a biomass agriculture waste and plant. It is important

to know that nearly 40% of chemical contents in grassy and woody plant extract consist of

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carbohydrate compounds rather than 20% lignin [4]. Such compound so-called as lignocellulose
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or lignin-carbohydrate complexes (LCC). Rice straw from paddy plant leftover is one of the
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sources of lignocellulose. From the previous report, the use of lignin as a corrosion inhibitor from
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oil palm fruit bunch [5], electropolymerized lignin [6], standard alkali lignin [7] and lignin
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terpolymer [8] have been successfully identified. A review of a study of corrosion inhibitor for
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ferrous and non-ferrous metal alloy in ionic sodium chloride solution has been reported [9,10].

The extract of rice bran has been studied by Dong et al. (2011) as a corrosion inhibitor for carbon
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steel in 1 M HCl [11]. They found that rice bran which contain phytic acid has increase the

inhibition efficiency as the extract concentration increased. A report by Zulkafli et al. (2013) were
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discussed about the use of rice straw extract as corrosion inhibitor in acid medium, HCl in the
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presence of surfactant. They examined the efficiency of rice straw extract with the influence of

temperature and various surfactants [12]. Recent study by Mahross et al. (2016) has found that the

use of rice straw extract in HCl gave high inhibition efficiency on mild steel corrosion. They stated

that the main compound in rice straw contains lignin [13]. However, all the work mention above

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was limited to the studies in acid medium. To the best of our knowledge, there are no results or

data reported on the use of rice straw extract in inhibiting the corrosion of steel in sodium chloride

environment.

Previously, we reported the inhibitory effect of lignin commercial in water medium [14].

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The result showed that low-carbon steel corrosion was inhibited in prolonged exposed in water

containing lignin. A moderate efficiency of 53% was attained on day-21 immersion. For that

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reason, other sources of natural lignin and different medium (NaCl) need to be adapted in new

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effort to enhance the efficiency. In this present work, RSE and commercial lignin were used as a

corrosion inhibitor for low-carbon steel corrosion in 3.5% NaCl solution. Lignin was used as a

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comparison study. The experiment has been performed at room temperature and atmospheric
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pressure. An inhibitory phenomenon was investigated through the formation of a protective layer
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on metal surfaces. All the results were characterized via Fourier Transform Infra-Red spectroscopy
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(FTIR), Variable Pressure-Scanning Electron Microscope VPSEM-EDX and X-Ray Diffraction

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(XRD).
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EXPERIMENTAL
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Preparation of steel sample

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Metal specimens used in this study was SAE1045 low-carbon steels (Metal Supply Company

Ziqrah Scientific, Malaysia) with a chemical composition (in wt%) of 0.12% C, 0.5% Mn, 0.04%
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P, 0.04% S and the remainder Fe. Steel specimens were trimmed to form a coupon of 1.2 cm

diameter disc with 1.5 mm diameter holes for suspension during immersion test. The steel was

ground using silicon-carbide paper with 400, 600, 800 and 1200 grit size and polished to obtain a

mirror-like surface. The polished steel surfaces were cleaned using water and acetone and dried

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immediately. The specimen preparation procedure was performed according to ASTM G1-03

standard [15].

Extraction of rice straw

The extraction method was performed through solvent extraction methods [16,17]. Rice straw was

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obtained from paddy field of Northern Peninsular of Malaysia. The straw was washed, dried and

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ground into a smaller size. The powder of straw was sieved to micron-sized, 500 μm. The powder

was then soaked in 60/40 of ethanol/water system with 0.01 M of sulphuric acid (QRëc, Malaysia)

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as a catalyst. The mixture was stirred at 60 °C on a hotplate for 3 hours. The extracted solution

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was filtered under vacuum pump. The ethanol solution in the filtrate was then removed using a

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rotary evaporator. At this stage, the final solution remained water and lignocelluloses compound.
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The solution was then frozen and dried under vacuum. A powder of RSE was obtained and stored
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in airtight container.
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Preparation of corrosion inhibitor solution

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A corrosion inhibitor solution containing RSE was prepared by weighing about 1.5 g of RSE

powders, mixed and dissolved it using distilled water and NaCl (Systerm, Malaysia) solution in a
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1L flask on a stirrer plate. Finally, the inhibitor solutions containing RSE were ready to use at 1500
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ppm or 1.5 g/L in 3.5% NaCl medium. Corrosion inhibitors containing commercial lignin (Sigma-

Aldrich, Malaysia) was also prepared in the same concentrations.

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Weight loss method

The initial weight of coupons was measured prior to the immersion. Metal coupons were immersed

in 3.5% NaCl medium without and with RSE and lignin for 7, 14, 21, 28, 35 and 42 days at room

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temperature (25°C) and exposed to the atmosphere. Initial pH was measured on day-0, 7, 14, 21,

28, 35 and 42 after the coupon was withdrawn from the test solution. The coupons were cleaned

and the final weight was measured. The method for the immersion corrosion test was conducted

according to a standard practices ASTM G31-72 [18]. The corrosion inhibition efficiency, IE%

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was calculated using the following equation:

 Wi 
1  

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IE%   100
Inhibition efficiency, (1)
 W0 

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with Wo = weight loss of uninhibited steel (mg), Wi = weight loss of inhibited steel (mg)

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K ΔW
Corrosion rate, CR (mm/y) = (2)
A tρ N
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with K = constant (8.76 x 104), t = exposure time (hr), A = area of exposure (cm2), ΔW = weight
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change (mg) and ρ = density of the metal specimen (g cm-3).

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Surface and morphology analysis

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Images of steel coupons were observed through an optical camera (Canon EF-S60mm f/2.8

Macro USM). Variable Pressure-Scanning Electron Microscope (VPSEM Leo Supra 50 VP) was
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used to obtain a clear image of the coupon surface in microscale. Both images were analyzed to

observe the physical appearance of uninhibited and inhibited steel samples. Surface analysis via
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Electron Diffraction X-Ray (PANalytical X’Pert PRO MRD PW3040) (EDX) was performed to

identify the elemental composition of corrosion product. Determination of corrosion product

phases XRD analysis was done via X-Ray Diffraction D8 Advance, Bruker AXS Germany,

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powered with 40kV and 1-D fast detector (Lynx-Eye). The data were analyzed via EVA software.

Analysis through FTIR (Perkin Elmer Spectrum 400, FT-IR/FT-NIR & Spotlight 400 Imaging

System) was conducted to identify the presence of functional groups of corrosion product and

complexes.

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Electrochemical test

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Cyclic polarization measurement was used to measure the corrosion of steel and to study the

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tendency of pitting on the specimen in the absence and presence of RSE and lignin. A low carbon

steel, carbon electrode and a saturated calomel electrode (SCE) were used as a working electrode,

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counter electrode and reference electrode respectively. An initial delay was performed at 20

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minutes prior to each measurement in order to establish a steady-state open circuit potential. Cyclic
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polarization measurements were carried out by sweeping the potential from the starting potential,
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-1.2 V (SCE), into the positive direction, at a scan rate of 1 mV s-1 up to the end potential, -0.5 V

(SCE), and then reversed with the same scan rate. The forward and reverse scan were finished until
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the hysteresis loop obtained. These measurements were carried out using a GAMRY
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potentiostat/galvanostat model potentiostat-galvanostat GAMRY 3.2 (CMS 105 Gamry

Framework Version 3.20). The inhibition efficiency (IE) was calculated according to the Tafel
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polarization method using the following equation:

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 
 I corr
i

IE  1    100 (3)
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 I corr o 
 
where Icorr i and Icorr o are the corrosion current densities in the presence and absence of inhibitor,

respectively.

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RESULTS AND DISCUSSION

Weight loss study

Fig. 1 represents the corrosion rate of low-carbon steel in NaCl solution without and with

inhibitors of RSE and lignin. Corrosion rates of uninhibited steel in NaCl alone showed the highest

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values at all durations of immersion compared to a system containing inhibitors. A steel in RSE

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inhibitors showed the lowest corrosion rate which was below 0.12 mm/y within 7 to 42 days

immersion. The corrosion rate of steel in NaCl solution containing lignin inhibitors was higher

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than RSE and there was an increment in the values from 28 to 42 days immersion. This finding

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suggested that the lignin inhibitors were unable to maintain the inhibiting action throughout the

period of immersion compare to RSE. N

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Fig. 2 indicates the corrosion inhibition efficiency of steel by RSE and lignin after

immersion in NaCl medium. Increases in inhibition efficiency mean decreases in weight loss and
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corrosion rate of the metal specimen. The efficiency of the RSE showed a sharp increase on day-
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7 to 14 and became consistent with efficiency exceeding 85% after 14 to 42 days. Meanwhile, an
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inhibition efficiency of lignin from 7 to 42 days immersion was gradually decreased from 68% to

11%. This is due to the loose and weak of adsorption properties since only lignin compound
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contributed to inhibition rather than RSE which contain celluloses. The weak adherence of

inhibitors film caused the steel surface underneath of the film become corroded and occupied with
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corrosion products, thus decreased the protection ability.

Extension of immersion time of steel in lignin inhibitor in the exposed atmosphere

increased the rate of corrosion due to the increased in the level of dissolved oxygen [19,20] and

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carbon dioxide concentration [21,22]. As a consequence, the additional sources of H+ ion

originated from carbonic acid, H2CO3 presence in dissolved carbon dioxide would be the factors

of decreased inhibition efficiency. By comparing with lignin inhibitors, RSE containing

lignocellulose compound was able to maintain the corrosion inhibition up to 42 days immersion

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due to the larger polymer structure.

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Fig. 3 shows the pH values of NaCl solution without and with corrosion inhibitor of RSE and

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lignin at 0 to 42 days. NaCl solution alone exhibited a slight increase in pH with increasing

immersion time of steel. The original pH of NaCl solution (pH =5.7) changed to pH 6.8 after 42

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days immersion.
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Corrosion inhibitor containing polymer compound would normally undergo hydrolysis

when reacted in acidic, alkaline and neutral solution [23,24]. Hydrolysis might cause corrosion
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inhibitor changes in pH. This phenomenon occurred after the water molecule (H2O) is hydrolyzed
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into hydrogen cations (H+) and hydroxyl anion (OH-). Certain parts of the polymer molecules will

be attracted to H+ and some others will be attracted to OH-. Meanwhile, NaCl will be hydrolyzed
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into Na+ and Cl-. Some of these ions will be reacted with water molecules and corrosion inhibitor
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molecules. The cation of Na+ which may react with both OH- and Cl- ion may associate with H+

and normally will produce a neutral solution or a salt.

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Nevertheless, the presence of the inhibitor molecules may decrease or increase the pH of

the solution. This phenomenon explained the consistency of inhibition efficiency value in RSE

whereby the hydrolysis of large polymer compound might stabilize the RSE inhibitors solution.

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Thus, RSE was able to maintain the inhibition efficiency throughout the immersion period. The

RSE inhibitors showed an almost consistent pH value, approaching neutral from 7 to 42 days.

While lignin inhibitors showed a slight increase in the pH value during the immersion of steel from

7 to 42 days. Although the alteration in the pH value of the lignin inhibitor was not much

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noticeable, it gave a significant change to the inhibition efficiency. Inhibition efficiency was found

to decrease with a slight increase in pH of lignin solution. This situation signified that the lignin

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provided weak corrosion protection such as small coverage and weak adsorptivity on metal

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interface compared to RSE.

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Surface and Morphology Study

Surface observation via optical images N

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Fig. 4 shows the image of steel surfaces in NaCl for 7 to 42 days. Immersion of steel in the
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NaCl without inhibitor (Fig. 4a-d) exhibited a very rough surface accompanied by the formation

of corrosion products. Typical corrosion products formed on steel which resulted from immersion
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in aqueous NaCl were identified as iron hydroxide, iron oxide, ferrous chloride salts and hydrated
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iron oxides.
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Steel surfaces exposed in NaCl containing RSE (Fig. 4e-h) were found to be covered by a
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thin organic protective layer obviously at 21-day immersion (Fig. 4g). The protective layers

become thicker and blackish color due to longer immersion time up to 42 days (Fig. 4h). The layer
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seemed strongly adsorbed on the steel surface compared to the specimen in the lignin solution.

The observed image was in line with 92% inhibition efficiency for 42 days immersion in RSE as

referred to Fig. 2.

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 A steel immersed in NaCl solution containing the lignin inhibitors for 14 days (Fig. 4j) also

formed a thin protective layer which almost covered the entire surface of the specimen. After 21

days of immersion, the protective layer turned into a blackish color (Fig. 4k). It was signified that

the blackish protective layers were mixed with both ferric and complexation organic compounds

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thus produced the ferric-lignin film. However, the layers were cracked and detached out from the

steel surfaces after 42 days (Fig. 4l). This situation explained the low inhibition value of 11%

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efficiency (Fig. 2). The brownish oxide formed on the steel surface immersed at 42 days known

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as hydrated iron oxides Fe2O3.H2O or Fe2O3. A little blackish oxide on the corroded surface might

be signified as magnetite, Fe3O4. These compounds were identified via XRD and were discussed

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in next subtopic.

Identification of morphology and corrosion products

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SEM micrographs presented in Fig. 5 corresponds to the steel surfaces immersed in NaCl

alone for 7, 14, 21 and 42 days. A steel immersed for 7 days in NaCl (Fig. 5a) showed the presence
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of small clumps and irregularly shaped of corrosion products dispersed all over the surface.
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Extension of immersion time until day-14 increased the rate of corrosion. Corrosion
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products with broccoli-like structure were formed on the steel surface (Fig. 5b). The corrosion

products consisted of high elements of oxygen (O) as a result of corrosion reactions as confirmed
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by EDX spectrum (Fig. 6a and 6b). The corroded surface with irregular shape and the porous

structure were observed in the specimen of 21 days immersion (Fig. 5c). A corrosion product

seemed to grow and thicken after 42 days of immersion. A coral-like and finger-like structure (Fig.

5d) of the corrosion products were occupied on the surfaces. EDX results in Fig. 6 shows the

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highest composition of oxygen (O) on the corroded surface, especially at 21 days corresponded to

a large amount of corrosion product formation (Fig. 6c). Other detected elements were originated

from low-carbon steel and FeCl2.

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SEM micrograph of steel surfaces after 7 days in RSE (Fig. 7a-d) shows the rough and gross

structure of ferric-RSE compound covered the steel surface. The crust of mixed oxide and

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complexation compound looks more evenly layered on the steel surface at 42 days of immersion

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compared to 7 days. The specimen surfaces were analyzed via EDX and showed that O was the

second highest element presented after Fe.

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The presence of carbon (C) elements was derived from the RSE, which was identified on
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the steel surface at 14 days of immersion (Fig. 8b). This result was in line with the %IE data which
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showed 87% inhibition (Fig. 2). However, there was no C element detected on the others steel
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surfaces on 7, 21 and 42 days even though the steel corrosion was inhibited by RSE. This is due
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to the fact that the surface was covered by a thick oxide layer which dominated the RSE and others

salt compound.
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Fig. 9 shows the SEM images of inhibited steel in lignin inhibitor. Immersion on day-7
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exhibited gross structures (Fig. 9a) accompanied by the growth of oxide on the surface after 14

and 21 days immersion (Fig. 9b and 9c). Extension of immersion time until day-42 caused the
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formation of corrosion products with finger-like structure (Fig. 9d). The oxide (O) formation on

the inhibited surface at day-7 was lesser than another specimen as observed through EDX analysis

(Fig. 10a-d). This result correlated with the decreased in inhibition efficiency as increase

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immersion time which promoted the corrosion reaction or oxide formation. The element of C was

originated from lignin and shows higher at day-7. The prolonged immersion of steel until 42 days

caused Cl to appear significantly as corrosion products (Fig. 10d).

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Identification of element and phase of corrosion products

Fig. 11(a) shows the XRD result of inhibited steel in RSE. The peak intensity of Fe was greatly

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diminished on day-14. The steel surface was also accompanied by the formation of corrosion

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products, magnetite (M), Fe3O4 at 35.3 (2θ). Magnetite is stable and has strong adhesion to metal

surfaces and cause a relatively impermeable layer against corrosion process. The increased in

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immersion time up to 42 days showed the steel surface almost was entirely covered by the ferric-

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RSE compound in the presence of magnetite (35.4 and 61.8 (2θ)) and lepidocrocite (27.1 and 39.6
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(2θ)).
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A low signal of the salt compound, FeCl2 (S) was detected after 42 days immersion at 46.7
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and 55.9 (2θ). Hamdy and Gendy have identified FeCl2 phase presented at 46.5 and 55.8 (2θ) on
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steel in chloride solution [25]. Such compound was preferable to be formed due to the long
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exposure in NaCl solution. A study by Möller et al. reported that the mineral halite salt derived

from 3.5% NaCl was found at 32 and 46 (2θ) showed by a sharp peak with high intensity and most
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of the oxide compounds were in crystal form [1].

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Fig. 11(b) shows the XRD pattern of inhibited steel in lignin. The signal intensity was very

low and showed a broad spectral pattern for all immersion times. Indeed, the intensity of the

detected peak was also decreased with the prolonged immersion. This phenomenon showed that

the corrosion product formed on the surfaces behaved as an amorphous compound. Nasrazadani

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stated that the phase transformation of iron rust is very fast for lepidocrocite, rather slow for

magnetite and very slow for goethite [26]. This condition is according to an agreement that an

organic protective layer may react with crystalline iron oxides and finally formed an amorphous

component [27]. Ferrihydrite (F) elements were detected approximately at 35.5 and 61.2 (2θ) was

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also detected on the inhibited steel surface in lignin. This element may appear in the presence of

dissolved organic material in which ferrihydrite was co-precipitated with organic materials [28].

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The elements of Fe was not detected because the surface was coated with a protective layer of

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ferric-lignin and oxide-hydroxide compounds.

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Identification of corrosion products and complexes compound
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FTIR spectrum of uninhibited steel in NaCl after 7 to 42 days is shown in Fig. 12(a). The
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formation of lepidocrocite (γ-FeOOH) was clearly visible when the immersion time was extended

up to 42 days. A study by Hu et al. stated that immersion of steel on day-2 caused the formation
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of more lepidocrocite compares to other periods of immersion [29]. Others found that lepidocrocite
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appeared significantly on steel after 10 days [5] and 21 days [1] immersion. The current result
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showed that the lepidocrocite peak was more apparent in 21 and 42 days.
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The formation of goethite (α-FeOOH) was clearly observed with a broad peak at 7 to 21 days

immersion. The presence of C-O group at around 1340, 1500 and 1650 cm- 1 on day-7, 14 and 21
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signified as carbonate compound. The dissolved carbon dioxide, CO2 reacted with salt water to

form carbonic acid, H2CO3 (Equation 4). The hydration reaction might cause a dissociation of

carbonic ion, HCO3– as shown in Equation 5. Thus, steel immersed in a salt solution which was

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exposed in the atmosphere led to the formation of iron carbonate, FeCO3 (Equation 8). Several

studies have reported on this reaction [30,31].

CO2 (aq) + H2O ↔ H2CO3 (aq) (4)

H2CO3 (aq) ↔ H+ + HCO3- (5)

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HCO3- ↔ H+ + CO3 2- (6)

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Fe ↔ Fe2+ + 2e- (7)

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Fe2+ + CO3 2- ↔ FeCO3 (8)

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Immersion of steel in NaCl after 42 days reduced the carbonate compounds and enhanced the
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formation of oxide-hydroxide complex. FeCO3 is soluble in aqueous solution at low temperature
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and remain oxide-hydroxide on steel surface.
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FTIR spectrum (Fig. 12(b)) of inhibited steel in RSE on day-7 signified a very little corrosion
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product formed on the steel surface. A signal peak for lepidocrocite, 1016 cm-1 distinctly appeared
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in 14, 21 and 42 days immersion. A very low intensity of goethite at 699 and 882 cm-1 indicated a

very few amounts of goethite existed compared to the corrosion product on steel in NaCl alone.
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No goethite was detected on 42 days immersion, assigned a good character of RSE as steel
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corrosion inhibitor. The immersion of steel in RSE solution might inhibit the formation of

corrosion products hence provide long-lasting protection. A signal peaks at around 1500 to 1300
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cm-1 represented an organo-metallic bonding of C=C−Fe and C=O−Fe due to a complexation

product of RSE and a metal ion.

Fig. 12(c) shows the FTIR spectrum of corrosion products on inhibited steel in lignin. A

peak around 1019 cm-1 represented as lepidocrocite was slightly appeared on day-7 and was

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diminished by increased immersion time. The elements of goethite (α-FeOOH) detected around

848 to 802 cm-1 was also reduced up to 42 days immersion. Formation of ferric-lignin as a thin

protective layer was clearly observed at day-7 around 1476 cm-1 and 1346 cm-1. However, the

presence of ferric-lignin compound was reduced on 14, 21 and 42 days immersion due to the

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growth of thick oxide-hydroxide compound on the steel surface.

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Cyclic polarization test

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Fig. 13 shows the cyclic polarization curves of steel in NaCl without and with RSE and

lignin inhibitors. The NaCl curve without inhibitors shows the active-passive region indicating the

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active and passive corrosion process happened on the steel surfaces. In cathodic polarization,

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oxygen reduction reaction occurs. While along the anodic polarization, steel specimens undergo
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oxidizing processes, passivation, partial passivation, repassivation and transpassive reactions.
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When the anodic polarization current is increased, a partial passivation state occurs around
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the current density of -4.7 A cm-2 at the potential of -0.76 mV, however, the process was no longer.

The formation of incomplete thin oxide layers at the partial passivation state has destroyed by the
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increase in current density up to -4.0 A cm-2. In passive conditions, the metal surface is enclosed
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with oxides in uneven form. The oxide layers were weakly absorbed and easily corroded and

dissolved at certain potential and density. The formation and breakdown of the oxide layer during
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cyclic polarization in corrosion medium have also been reported by Amin et al. (2010). The

dissolved oxide replaced by absorbed anion causes the formation of thin and porous passive films

[32]. The condition causes the oxide layer was occupied temporarily and dissolve along with the

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increase in current density. The polarization of the steel in a more positive anodic potential causes

steel to undergo pit propagation [33].

From the tabulated data in Table 1, Epit NaCl> Epro NaCl signifying the steel are exposed

greatly to pitting corrosion [34]. With the use of inhibitors, the Epit values become more positive.

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The result agreed with a report by [35], which stated that the organic corrosion inhibitors could

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inhibit pitting corrosion based on the change in the value of the Epit to a more positive value

compared to the system without inhibitor. The indication of high corrosion on steel is shown

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whenever the value of Ecorr> Epro [33,36]. The value of Ecorr for both RSE and lignin were

smaller (less positive or more negative) than Epro for each system. This indicates the corrosion

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was inhibited. The inhibition efficiency data revealed that the inhibition was at 53% for RSE and

only 37% for lignin.

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With the use of RSE inhibitors, the hysteresis loop of RSE shown in Fig.13(a) was smaller
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than the NaCl loop. This signified RSE still capable to inhibit pitting corrosion even though Epit
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RSE is higher than Epro RSE. A clear signal of pitting potential (Epit RSE) are almost invisible
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indicating the activation polarization continue to occur without creating an active-passive

corrosion region. However, the value of Epit RSE still can be detected at -0.52 mV. The reversible
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scan showed the value of Epro RSE at -0.63 mV and exhibits decreased in size of the hysteresis
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loop.

Meanwhile, for the system in lignin inhibitors (Fig. 13(b)), the cathodic slope is almost
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constant and this indicates the occurrence of a concentration polarization. Increase in anodic

polarization indicating the increase in activation polarization thus enhance the oxidation. The

values of Epit lignin were shown at -0.49 mV and almost unseen in the plotted graph, and the

density of the currents were increased afterward. Subsequently reaching the reverse potential at -

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0.33 mV, the hysteresis loop crossed on the anodic slope, and reaches Epro lignin at -0.64 mV.

The hysteresis loop sizes were smaller than the NaCl one. Epit lignin > Epro lignin indicates that

pitting corrosion is still present. However, the difference between Ecorr lignin and Epro lignin is

very small and this shows that the development of new pit can be stopped immediately and the

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corrosion process can be inhibited.

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Corrosion Inhibition Mechanism

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The inhibitory mechanism of steel corrosion by the RSE in NaCl medium was proposed as

illustrated in Fig. 14(a)-(d). As shown in Fig. 14(a), in a corrosion inhibitor solution having organic

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compound, the inhibitor molecules will be protonated (H+ RSE) once contacted in aqueous

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solution. Anions and cations in bulk solution were moving around and some specific ions will
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move and be attracted towards the interface. Fig. 14(b) showed the formation of hydroxide
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protective layer and the interaction of inhibitors on the steel surface. Since the steel surface

provides more electrophile properties (positively charged), therefore Fe2+ attracts the OH- and Cl-
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anions through ionic bonds. Meanwhile, an interaction of Van der Waals will be created within
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protonated inhibitors (H+ RSE) and adsorbed Cl- ions.

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Generally, steel will first experience the corrosion process (Equation 9-11) and form a layer

of ferrous hydroxide, Fe(OH) 2 which is a less stable oxide (Equation 12).

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Fe (s) → Fe2+ (aq) + 2e (9)

O2 (g) + 2H2O (l) + 4e- → 4OH- (aq) (10)

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 2Fe (s) + O2 (g) + 2H2O (l) → 2Fe 2+ (aq) + 4OH- (aq) (11)

Fe 2+ (aq) + 2OH- (aq) → Fe (OH)2 (s) (12)

This protective layer can be converted to other oxides known as magnetite (Fe3O4), which

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is relatively stable during the dissolution process of Fe (OH)2 after prolong exposed to corrosion

agent (Equation 13). A more stable hydroxide, which is hydrated iron oxide, Fe2O3.xH2O will be

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formed after continuous exposure to corrosive medium (Equation 14).

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3Fe (OH) 2 (s) → Fe3O4 + H2 + 2H2O (l) (13)

2Fe (OH) 2 (s) + (x-1) H2O (l) → Fe2O3.xH2O (s) + 2H+ (aq) + 2e (14)

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During the oxide-hydroxide formation, the RSE molecules move near the interface region
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to occupy the steel surface which was adsorbed by Cl- ions. Since Fe(OH)2 was considered not
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stable, a pit or pores on the oxide layer were easily formed. The RSE molecules adsorbed in the

pores and cover up the pores to prevent further corrosion. The penetration of pore by the Cl- gave
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benefit to the RSE molecules by providing a space for specifically adsorption to inhibit the
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corrosion process. The magnetite layer which was continuously immersed in a solution might
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corrode and form a protective coating which was more stable Fe2O3.xH2O (Fig. 14(c)).

The remaining RSE molecules on the surface of the oxide layer will continue to occupy
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the pores and lock up the active site for corrosion. Meanwhile, complexation reactions occur in

the bulk solution. Anions, cations and H+RSE molecules which initially failed to adsorb over the
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steel surface turned to form a complex of ferric-RSE. Finally, they adsorbed on the surface of the

outermost layer and developed as an oxide-hydroxide-inhibitor component. These situations create

the geometry of protective multilayer on the surface of the steel (Fig. 14(d)). The formation of a

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complexes compounds (ferric-RSE) on the inhibited steel in RSE was proven by FTIR and XRD

analysis.

The adsorption of RSE on the steel surfaces was identified to behave as interphase

inhibition, which involved the formation of a protective film on the 3-dimensional metal surfaces.

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This protective film possessed less soluble multilayer adsorbent which consisted of oxide-

hydroxide, salt or other reaction products formed through the reaction of anion and cation inhibitor

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near the metal surface. The interphase film served as a physical barrier to block or inhibit transport

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processes and kinetics reaction of corrosion on metal surfaces. The presence of RSE molecules

together with corrosion products created the cooperative-inhibition. Adsorption mechanism may

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involve physical adsorption and follow by chemical adsorption [5]. The almost similar occurrence
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of such complexes was ferric-lignin compounds, that was reported to be adsorbed on the oxide
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layer which was initially formed in the steel surface to prevent penetration of chloride ions [37].
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The formation of a thick oxide layer on the surface of stainless steel has been cooperated with
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inhibitors to reduce corrosion in NaCl medium. The inhibitor molecules form a protective layer
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over oxide-hydroxide layer.

In our study, the ferric-RSE was suggested to adsorb on the steel surface by physical
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adsorption. The inhibitors molecule reacted on the steel surface incorporated with the oxide-
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hydroxide film. The inability of protective film to maintain the strength of adsorption against the

prolonged immersion was the factors of weak adsorption properties compared to chemisorption
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one. Film-forming corrosion inhibitors, which inhibited at the interphase, formed a porous

protective layer. Therefore, corrosion inhibition efficiency was highly dependent on the nature of

the layer 3-dimensional shape, porosity and stability [3]. The 3-dimensional layer porous oxide

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could be formed in a neutral medium in the presence and absence of oxygen. Those phenomena

made the RSE were adsorbed unevenly on steel surfaces.

CONCLUSION

In this study, RSE showed an excellent corrosion inhibitor in NaCl medium. The overall findings

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can be concluded as below:

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 The RSE capable of inhibiting the corrosion of steel in NaCl up to 42 days of immersion

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and provided 92% inhibition efficiency compared to commercial lignin.

 RSE performed the acceptance ranges of corrosion rate values which is about 0.12 to 0.013

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mm/yr along 42 days in NaCl exposure. The pH values of RSE solution systems showed
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the insignificant effect on the inhibition efficiency.
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 FTIR results revealed the formation of lepidocrocite and magnetite as corrosion products
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on steel surface was reduced after immersion in both RSE and lignin. The organo-metallic

compounds formed on the steel surface provided a barrier for metal dissolution thus
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behaved as a corrosion inhibitor.

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 Surface analysis via optical camera and SEM-EDX revealed the emergence of a ferric-RSE
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layer. The protective layer was temporarily adsorbed and easy to detach after prolonged

immersion. XRD analysis showed the formation of corrosion products (oxide-hydroxide)

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on steel could be reduced with the use of RSE in NaCl medium and at the same time

assisted the corrosion inhibition.

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 Through the cyclic polarization measurements, the use of RSE inhibitors be able to inhibits

the pitting corrosion by presenting the value of Ecorr RSE < Epro RSE, and reduction in

the size of hysteresis loop between RSE and NaCl.

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  The inhibitory mechanism was proposed to be achieved through interphase inhibition,

which involved the co-operation of oxide-hydroxide formation on carbon steel surfaces.

The combination reaction within the oxidation of steel, complexation of organo-metallic

compound and adsorption contributed to an excellent inhibition of low-carbon steel

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corrosion.

AUTHOR INFORMATION

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Corresponding Author

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Email: solhan.yahya@utp.edu.my Phone: +60 5368 8305. Fax: +60 5368 8307

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Notes

The authors declare no competing financial interest. N

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ACKNOWLEDGMENTS
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The authors would like to thank the Ministry of Science, Technology & Innovation, Malaysia
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(MOSTI) for the financial support given through the Sciencefund Grant Scheme (03-01-02-
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SF0734). S.Yahya would like to thank the Ministry of Higher Education, Malaysia (MOHE) for

their support through MyBrain15 (MyPhD) scholarship.

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REFERENCES
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[1] H. Möller,, E.T. Boshoff,, H. Froneman, J. South African Inst. Min. Metall. 106 (2006)

585–92.
A

[2] A.A. Rahim,, J. Kassim, Recent Patents Mater. Sci. 1(3) (2008) 223–31.

[3] W.J. Lorenz,, F. Mansfeld, Electrochim. Acta 31(4) (1986) 467–76.

[4] R. Sun, BioResources 4 (2008) 452–5.

[5] E. Akbarzadeh,, M.N.M. Ibrahim,, A.A. Rahim, Int. J. Electrochem. Sci. 6 (2011) 5396–

22
 416.

[6] M.Y. Vagin,, S.A. Trashin,, A.A. Karyakin, Electrochem. Commun. 8 (2006) 60–4.

[7] A. Altwaiq,, J. Khouri,, S. Al-luaibi,, R. Lehmann,, H. Drucker,, C. Vogt, J. Mater. Environ.

Sci. 2(3) (2011) 259–70.

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[8] Y. Ren,, Y. Luo,, K. Zhang,, G. Zhu,, X. Tan, Corros. Sci. 50(11) (2008) 3147–53.

[9] C. Verma,, E.E. Ebenso,, M.A. Quraishi, J. Mol. Liq. 248 (2017) 927–42.

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[10] K. Xhanari,, M. Finšgar, Arab. J. Chem. (2016).

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[11] L. Dong,, L. Yuanhua,, D. Yigang,, Z. Dezhi, Anti-Corrosion Methods Mater. 58(4) (2011)

205–10.

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[12] R. Zulkafli,, N.K. Othman,, A. Jalar, AIP Conf. Proc. 48 (2013) 48–53.

N
[13] M. Mahross,, A. Naggar,, T. Seaf Elnasr,, M. Abdel-Hakim, Chem. Adv. Mater. 6(16)
A
(2016) 6–16.
M

[14] S. Yahya,, N.K. Othman,, A.R. Daud,, A. Jalar, Sains Malaysiana 42(12) (2013) 1793–8.

[15] ASTM G1-03, Standard Practice for Preparing, Cleaning, and Evaluation Corrosion Test
D

Specimens, 1999.
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[16] H. Belanger, Pat. Appl. Publ. US 2009/00(8) (2009).

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[17] R. Sun,, J.M. Lawther,, W.B. Banks, Ind. Crops Prod. 6(1) (1997) 1–8.

[18] ASTM G 31-72, Standard Practice for Laboratory Immersion Corrosion Testing of Metals,
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Vol. 72, 2004.

[19] V.S. Sastri,, E. Ghali,, M. Elboujdaini, Corrosion Prevention and Protection Practical
A

Solutions, JohnWiley & Sons, Ltd, West Sussex, England, 2007.

[20] V.S. Sastri,, J.R. Perumareddi, Corrosion (1994) 9312.

[21] M. Nordsveen,, S. Nes, Corrosion 59(5) (2003) 443–56.

23
[22] F.F. Eliyan,, A. Alfantazi, Corrosion 9312 (2014) 880–98.

[23] A. Rahim,, E. Rocca,, J. Steinmetz,, M. Jain Kassim, Corros. Sci. 50(6) (2008) 1546–50.

[24] L.A. Al Juhaiman,, A.A. Mustafa,, W.K. Mekhamer, Anti-Corrosion Methods Mater. 60(1)

(2013) 28–36.

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[25] A. Hamdy,, N.S. El-Gendy, Egypt. J. Pet. 22(1) (2013) 17–25.

[26] S. Nasrazadani, Corros. Sci. 39 (1997) 1845–59.

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[27] A. Collazo,, X.R. Nóvoa,, C. Pérez,, B. Puga, Electrochim. Acta 53(25) (2008) 7565–74.

SC
[28] D.L. Sparks,, C. Chen, in: J. Xu, J. Wu, Y. He (Eds.), Functions of Natural Organic Matter

in Changing Environment, Springer Netherlands, Dordrecht, 2013, pp. 7–12.

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[29] J. Hu,, S. Cao,, J. Xie, Anti-Corrosion Methods Mater. 60(2) (2013) 100–5.

N
[30] V.M. Abbasov,, H.M. Abd El-Lateef,, L.I. Aliyeva,, E.E. Qasimov,, I.T. Ismayilov,, M.M.
A
Khalaf, Egypt. J. Pet. 22(4) (2013) 451–70.
M

[31] M. Aminul Islam,, Z.N. Farhat,, E.M. Ahmed,, A.. Alfantazi, Wear 302(1–2) (2013) 1592–

601.
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[32] M.A. Amin,, Q. Mohsen,, G.A.M. Mersal, Port. Electrochim. Acta 28(2) (2010) 95–112.
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[33] U. Trdan,, J. Grum, Corros. Sci. 59 (2012) 324–33.

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[34] A. Poursaee, Electrochim. Acta 55(3) (2010) 1200–6.

[35] Amin, Corros. Sci. 52(10) (2010) 3243–57.

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[36] M. Finšgar,, S. Fassbender,, F. Nicolini,, I. Milošev, Corros. Sci. 51(3) (2009) 525–33.

[37] E. Almeida,, D. Pereira,, M.O. Figueiredo,, V.M.M. Lobo,, M. Morcillo, Corros. Sci. 39(9)
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(1997) 1561–70.

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Fig. 1. Corrosion rate of low-carbon steel corrosion in NaCl with and without RSE and lignin.

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Fig. 2. Inhibition efficiency of low-carbon steel corrosion in NaCl containing RSE and lignin.

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Fig. 3. pH of corrosion inhibitor solution in NaCl with and without RSE and lignin at 7 to 49 days.

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Fig. 4. The image of steel surfaces immersed in 3.5% NaCl containing RSE and lignin solution
after 7 to 42 days.

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Fig. 5. SEM micrograph of uninhibited steel in NaCl after (a) 7, (b) 14, (c) 21, (d) 42 days.

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Fig. 6. EDX spectrum of uninhibited steel in NaCl after (a) 7, (b) 14, (c) 21, (d) 42 days.

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 Fig. 7. SEM micrograph of inhibited steel in RSE after (a) 7, (b) 14, (c) 21, (d) 42 days.

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Fig. 8. EDX spectrum of inhibited steel in RSE after (a) 7, (b) 14, (c) 21, (d) 42 days.

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Fig. 9. SEM micrograph of inhibited steel in lignin after (a) 7, (b) 14, (c) 21, (d) 42 days.

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Fig. 10. EDX spectrum of inhibited steel in lignin after (a) 7, (b) 14, (c) 21, (d) 42 days.

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Fig. 11. XRD spectrum of inhibited steel in (a) RSE and (b) Lignin after 7 to 42 days.
Fe-Ferum, L- Lepidocrocite, M-Magnetite, G-Goethite, S-FeCl2.

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Fig. 12. FTIR spectrum of corrosion products on uninhibited steel in (a) NaCl (b) RSE and (c)
Lignin after 7 to 42 days.

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Fig. 13. Cyclic polarization curve of steel in NaCl without inhibitor and with inhibitor (a) RSE
and (b) Lignin

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Fig. 14. Illustration of proposed inhibitory mechanism of steel corrosion by RSE in NaCl. (a)
Various ions dispersed in bulk solution whereby anion of OH- and Cl- moving towards the steel
surface (Fe2+). (b) Formation of hydroxide protective layer Fe(OH)2 and the interaction of inhibitor
molecules (H+ RSE) in oxide pore. (c) Formation of oxide-hydroxide protective multilayer and
complexation reaction. (d) Adsorbed ferric-RSE complex on oxide-hydroxide protective
multilayer.

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 Table 1: Cyclic polarization parameter of steel in NaCl with RSE and Lignin

Inhibitor Ecorr Epit Epro Icorr IE%

NaCl -0.95 -0.53 -0.65 1.26 x 10-5 0
RSE -0.73 -0.50 -0.63 5.90 x 10-6 53
Lignin -0.65 -0.49 -0.64 7.94 x 10-6 37

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