Engineering Failure Analysis 100 (2019) 365–380

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Engineering Failure Analysis

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Corrosion inhibition of steel in multiple flow loop under 3.5% NaCl

T
in the presence of rice straw extracts, lignin and ethylene glycol
S. Yahyaa,b, , N.K. Othmana, M.C. Ismailb
⁎

a
School of Applied Physics, Faculty of Science and Technology, Universiti Kebangsaan Malaysia, Bangi 43600, Selangor, Malaysia
b
Centre for Corrosion Research, Department of Mechanical Engineering, Universiti Teknologi PETRONAS, 32610 Seri Iskandar, Perak, Malaysia

ARTICLE INFO ABSTRACT

Keywords: The investigation of steel corrosion has been done in a multiple flow loop (corrosion test rack)
Steel under hydrodynamic condition. Further, the performance of rice straw extracts (RSE), lignin (L)
Weight loss and ethylene glycol (EG) to inhibit the corrosion were studied through weight loss analysis. The
Erosion corrosion data has been tabulated based on the different position of steel specimen in corrosion test rack;
Flow loop
middle, elbow and the end of the rack. The initial study was performed at 30 °C of 3.5% NaCl
Surface analysis
alone and showed slight corrosion damage with the appearance of pitting and oxide growth. The
degradation of steel surface was depending on its position in the rack which experienced different
flow. A study at 40 °C with inhibitor solution revealed a significant inhibition. NaCl alone and EG
exhibited severe corrosion at the end of the rack. In contrast, the use of RSE and lignin inhibitors
reduced the corrosion attack significantly at the end of the rack. The effectiveness of the cor-
rosion inhibitors was depending on the chemical constituents, structure, functional groups as
well as the composition of the compounds. The order of the best performance of corrosion in-
hibitor was; RSE > L > EG. Localized pitting corrosion is a primary type of corrosion attack
before general and erosion-corrosion take place.

1. Introduction

Internal corrosion of the piping system is a serious metal degradation process. In addition to the cost involved, engineering effort
and maintenance phase were also extremely burdensome. Ineffective prevention and control of corrosion will cause problems, un-
expected plant shut down, production loss or more complicated whenever it engages with public health. Corrosion in the pipe due to
the acceleration or increase in the relative movement between a corrosive fluid and metal surface will cause erosion-corrosion [1].
Wall thinning on the interior surface of pipe wall results in leaking problem. Indeed, metal degradation also initially combined with
extensive localized and general corrosion. In dynamic form, the vigorous flow of fluid will easily degrade a metal component,
especially in valves, pumps and measuring devices including a nozzle, orifice and turbine blades [2]. Many of piping and plumbing
parts such as joints, elbows, connectors, caps, tees, cross and degree bends were usually exposed to the corrosion attack. Whenever it
has been completely fitted in the piping systems, an efficient monitoring has to be planned. A corrosion test rack is a common
simulator used in industries to monitor the progress of corrosion [3–5]. The use of test rack has been introduced in the industry due to
the practical means, fast and easy method of mimicking the real corrosion system.
Corrosion inhibitor remains a practical and cost-effective method of corrosion control in the monitoring piping system, depending
on good inhibitor selection. A study on corrosion inhibition of steel under dynamic condition involved complex blends of phosphorus,

⁎
Corresponding author.
E-mail address: solhan.yahya@utp.edu.my (S. Yahya).

https://doi.org/10.1016/j.engfailanal.2019.02.036
Received 7 May 2018; Received in revised form 23 January 2019; Accepted 14 February 2019
Available online 15 February 2019
1350-6307/ © 2019 Elsevier Ltd. All rights reserved.
S. Yahya, et al. Engineering Failure Analysis 100 (2019) 365–380

nitrogen and carboxylic acid containing corrosion inhibitors, film forming inhibitors [6], polyethylene amine [7], indole and cetyl
trimethyl ammonium bromides [8], amine and imidazoline [9] generally reports the influence of fluid flows stimulate the corrosion
mode. The inhibition of metal corrosion would be affected whenever metal surface contacted with the robust hydrodynamic en-
vironment. The accumulation of inhibitors molecules on the metal surface will improve the inhibition since there is an increase in
mass transport in the flowing condition. In contrast, others report a hydrodynamic condition also will decrease the inhibition per-
formance [10,11]. This happened by transporting the ions (Fe2+) from the metal surface to the bulk solution, hence overtake the
presence of [Fe inh]2+ complex on the metal surface. High velocity results in the separation of the adsorbed inhibitors layer due to an
increase in shear stress effects. Consequently, desorption of [Fe-inh]2+ complex occurred and the inhibition efficiency decreased. In
another report, a low speed may cause the formation of protective iron carbonate film on the entire surface of the elbows thus
decreased the corrosion rate [12]. The superflow of liquid affected the formation of corrosion product (protective film) on the metal
surface, increased in corrosion rate and exhibits uniform corrosion over the surface angles. While in the moderate flow, the protective
film formed in the localized areas of the elbow. These conditions promote the growth of pores film structure and a tendency to
corrode is high.
To the best of our knowledge, there is a limited report of erosion-corrosion associated with organic corrosion inhibitors, speci-
fically simulation in multiple pipelines. We present a different viewpoint of studies which indicates the used of organic inhibitors in
reducing the corrosion of steel at various steel position in a multiple flow loop. The novelty of this work is determining the behaviour
of corrosion and inhibition in multiple flow loop by observing the real texture or character of degraded steel treated in a dynamic
condition. In this study, the metal specimen will be exposed to the salt solution in the loop at the position of middle, elbow and end of
the test rack (multiple flow loop). The inhibition of steel corrosion will be evaluated by applying an organic inhibitor in the dynamic
system. An assessment of the corrosion attack was evaluated via corrosion rate and gravimetric analysis. The observation of corrosion
damage was mainly determined through high-resolution optical image and microscopic analyser.

2. Materials and methods

2.1. Preparation of corrosion inhibitor

Two chemicals and one raw material extract have been used as corrosion inhibitors; lignin (L) (Sigma-Aldrich, Malaysia), ethylene
glycol (EG) (Sigma-Aldrich, Malaysia) and rice straw extract (RSE) respectively. Rice straw was obtained from a paddy field in
Kodiang Kedah, Northern Peninsular of Malaysia. The straw has been extracted through solvent extraction at 60 °C of ethanol (QRëc,
Malaysia)/water mixture of 60:40 (v/v) for 3 h. About 1 ml of 0.01 M sulphuric acid (QRëc, Malaysia) been used as a catalyst in the
extraction process. The solvent was then evaporated and been freeze before the drying process. The yield was analysed using Fourier
Transform-Infrared (FT-IR) model Perkin Elmer Spectrum 400, in the range of 400 to 4000 cm−1. This analysis was performed to
identify the functional groups present in the RSE.
The Liquid Chromatography-Mass Spectroscopy, LCMS Dionex Ultimate 3000 was used to determine the compositions of the
chemical compounds in the sample. LCMS-grade of water was used to dissolve the sample. The separation was carried out in a C18
column packed with a cation exchange polymer and a solvent of 50%, v/v acetonitrile and methanol (containing 1.5% acetic acid)
were used as a mobile phase. The sample was auto injected at a flow rate of 0.7 ml m−1 with 2.0 bar of set nebulizer. The detection of
the molecular ion of each chromatogram peak was performed in a range of 150–2000 m/z using mass spec, MS Bruker Daltonic Micro
ToF.
The concentrations of both lignin and RSE inhibitor solutions were prepared at 1500 ppm. The solution of sodium chloride 3.5%
(Sigma-Aldrich, Malaysia) was used as a blank/control medium.

2.2. Corrosion test

A low-carbon steel coupon SAE1045 (chemical composition in wt%: C 0.12%, Mn 0.5%, P 0.04% and S 0.04%, Fe balance)
obtained from Ziqrah Scientific Malaysia, was used with an apparent surface area of 5.06 cm2. The coupon was polished with 600 to
1200 grit emery paper, washed with distilled water and dried according to the ASTM standard method [13]. The weight of the
coupon was measured before mounting the specimen in the loop.
The evaluation of steel corrosion was performed in designed corrosion test rack (Fig. 1) to simulate the multiple flow loop. Four
positions of the coupon in the rack have been chosen as a place to mount the coupon specimen; middle, elbow and end of the test rack
(Fig. 2). A corrosion test was subjected to dynamic flow in 30 and 40 °C for NaCl solution alone. The performance of the corrosion
inhibitor was tested at 40 °C. The dynamic conditions were controlled at a flow rate of 8 gpm (5 × 10−4 m3 s−1) for 3 h. The final
weight of steel coupon was measured to quantify the corrosion rates (CR) and inhibition efficiency (%IE) as Eqs. (1) and (2) below
[14,15]:

K × W
CR =
A × t × (1)

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Fig. 1. The position of metal samples mounted in test rack; a1–a4 for the middle position, b1–b4 for end position, c1–c4 for elbow position.

Fig. 2. Installation of coupons in corrosion test rack (a) middle, (b) end, (c) elbow.

CRi
%IE = 1 × 100
CRo (2)

where K is the unit-conversion constant (8.76 × 104), t is a time of exposure (h), A is the area (cm2), W is the weight loss (mg) and ρ is
the density of the metal (7.85 g cm−3). CRi and CRo are the corrosion rates of the steel coupon in the presence and absence of the
inhibitor, respectively.
The observation of corrosion effect on the specific region of steel surface was done via AXIO Microscope (10×/0.2 HD) Image
Analyser and a high-resolution optical camera. Scanning Probe Microscope (SPM), NTEGRA Prima NT-MDT was used to observe and
quantify the topography of steel surface.

Fig. 3. FTIR spectrum of the RSE and lignin.

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Table 1
Peak assignment of the FTIR spectrum for the RSE and lignin.
Wavenumber (cm−1) of the main peak detected in Wavenumber (cm−1) of a standard chemical Signal peak
this study sample [17]

RSE Lignin Lignin, cellulose and hemicellulose

1600 1585 1603 (lignin) 1600 cm−1 – Stretching CeC lignin aromatic ring
1634 (cellulose) [20,21];
1646 (hemicellulose) 1635 cm−1 – Stretching COOH aromatic [22].
1510 1510 1514 (lignin) 1510, 1513 cm−1 – Stretching C]C for aromatic
1508 (hemicellulose) lignin structure [20,23].
1376 1383 1367 (cellulose) 1370 cm−1 – Weak stretching CeO [20].
1380 cm−1 – CeH symmetry and asymmetry [23].
1235 1241 1203 (cellulose) 1246 cm−1 – Weak stretching CeO [20].
1212, 1252 (hemicellulose)
1047 1040 1034 (lignin) 1035 cm−1 – Vibration stretching CeO, C]C and C-C-
1044 (hemicellulose) O [24].
1045 cm−1 – Bending C-OH [22].

3. Results and discussion

3.1. Chemistry of RSE, lignin and ethylene glycol

The FTIR spectrums of RSE and lignin are shown in Fig. 3 and the peak assignments for each functional group were tabulated in
Table 1. Main signal peaks for RSE were observed at 1600, 1510, 1376, 1235 and 1047 cm−1 which shows the presence of lignin,
celluloses and hemicelluloses. Those detected signals are typical of lignocellulose compounds and have also generally been reported
by others [16–18]. The RSE obtained from the solvent extraction in this study were recognised as lignocellulose compounds. Lignin
sample also shows the results in the range of wavenumber with respects to the lignin sample reported elsewhere [17–19].
Fig. 4(a) shows the LCMS spectra of various chemical compounds in RSE and the structure of the major compound, as illustrated
in Fig. 4(b). LCMS investigation coupled with mass spectrometric analysis indicates the major compounds in the RSE was 4-Allyl-
syringol (2) (31.73%). The peak signals and the percentage composition of the chemical compounds in the RSE were compared with
others [25–27] and were summarized in Table 2.
Fig. 5 represents the LCMS spectra of lignin and the chemical structure of the major compound in lignin. The list of compound
presented in lignin was stated in Table 3. Coniferyl alcohol (14) was detected as a major compound with 38.97%.
Fig. 6 shows the general structure of ethylene glycol, HO-CH2-CH2-OH, with short aliphatic chain. Ethylene glycol has a large
molecule compared to water, thus it is able to be adsorbed on the steel surface [28,29].

3.2. Observation on corroded steel surface in 3.5% NaCl flow at 30 °C

Fig. 7 shows a graph of weight change of metal specimen at the different sample position. A specimen placed in the middle of the
rack having weight loss (61.1 mg) and the value of corrosion rate was 0.045 mm yr−1. Meanwhile, specimens at both end and elbow
experienced a minimum weight gained (about 3 mg). This is possible because as the metal corroded, the growth of oxide will happen.
Instead of corrosion, there is another reaction called ‘rusting’ associated during the experiment. In fact, rusting may increase the
weight of metal although the specimen has been properly cleaned after treated due to the very strong adherence of rust/oxide
product. The weight gain of copper alloy due to the oxide growth has been mentioned in the erosion-corrosion study [31], but have
not quantitatively reported. In our work, for the weight loss sample, it is suggested that the corrosion processes on the surface are

Fig. 4. (a) LCMS spectrum of the RSE; (b) Structures of the major compounds in RSE, 4-Allylsyringol.

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Table 2
Chemical composition of the compounds presented in the RSE extract.
Peak assignment Retention time (min) Compound Composition (%)

1 34.2 Anhydrosugar 3.17

2 34.7 4-Allylsyringol 31.73
3 35.9 4-Ethyl guaiacol 29.01
4 36.8 Syringaldehyde 0.27
5 37.2 Cis-coniferyl alcohol 16.77
6 38.6 4-Propyl guaiacol 12.39
7 39.0 Trans-coniferyl alcohol 5.30
8 41.8 Trans-isoeugenol 1.36

Fig. 5. LCMS spectrum of lignin and the structures of the major compounds in lignin, coniferyl alcohol.

Table 3
Chemical composition of the compounds presented in the lignin obtained via LCMS.
Peak assignment Retention time (min) Compound Composition (%)

1 3.3 3-Furaldehyde 12.03

2 20.68 2,4-Xylenol 4.89
3 21.03 m-Methylguaiacol 14.85
4 21.4 4-Methylguaiacol 1.88
5 22.24 Catechol 2.28
6 22.44 Coumaran 2.08
7 25.53 Homocatechol 1.74
8 26.05 4-Vinylguaiacol 2.58
9 26.43 5H-Furan-2-one 4.69
10 30.63 cis-Isoeugenol 5.59
11 43.83 Vanillin 0.73
12 44.2 Homovanillin 6.43
13 44.83 trans-Synapaldehyde 1.27
14 47.19 Coniferyl alcohol 38.97

influenced by shear stress [32,33] and turbulent flow which rises the mass transport of fluids towards and from the surface [34]. A
steel sample in the middle of rack suffered a laminar flow (Fig. 8a). The sample experienced a direct contact of a fluid stream, results
in lost the weight. Meanwhile, for the weight gain sample, this occurrence may be due to the differences in flow and movements of
the solution since the effect of erosion-corrosion also involved. The turbulent (Fig. 8b) and impingement flow (Fig. 8c) at both end
and elbow site respectively, experienced a vigorous movement of a solution containing sand particles. The almost similar effect of
erosion-corrosion also has been discussed through the study of sand fines erosion in a series mounted elbows [35]. The particle
impact was the main role for the change in solid particle erosion speed and angle. The solution stream transports the corrosion
products (resulted from erosion) and strongly attached to the metal surface. The rough surface of the corroded area at the end and
elbow provide a space for fine corrosion product to accumulate, hence increase weight.
A pictorial summary in Table 4 described the effect of corrosion at five different spots or regions focused on the specimen surfaces.
Region 1 indicated the images of distinctly/visible pits formed on each surface. Whilst, Region 2 focused on the invisible pit/
corrosion effect through the optical view on the specimen. Region 3 represented the corrosion damage at the edge of the specimen.
The most severe and mild corrosion attack was shown in Region 4 and 5 respectively. A specimen located in the middle of the rack

Fig. 6. Chemical structure of ethylene glycol [30].

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Fig. 7. Weight change of metal sample at a different position in corrosion test rack.

contacted with the laminar flows revealed severe corrosion at the edge of the specimen which contributed to the high weight loss.
Meanwhile, at the end and the elbow of the rack, the corrosion attack dominantly happened on the top surface accompanied by
cavities and pits. There is also an accumulation of corrosion products such as rust or oxide inside pits or cavity which typically FeCO3
grown on the surface and made the specimen gained weight. The oxide was strongly deposited on top of the specimen surface.

3.3. Analysis of corrosion rate of steel in 3.5% NaCl flow at 40 °C in the presence of corrosion inhibitors

Fig. 9 shows the corrosion rate values of steel specimens without and with inhibitor at different positions in corrosion rack. Steel
in NaCl solution shows the highest value of corrosion rate at all positions compared with the steel in inhibitors. The value was
significantly reduced by the presence of EG, followed by lignin and RSE inhibitors.
The variation in corrosion rate reduction at a different position of samples were shown for all the corrosion inhibitors. A steel
coupon in NaCl alone showed a higher corrosion rate at the end of the rack. The use of RSE showed the lowest corrosion rate as
compared to others inhibitors, particularly at the end of the test rack. The lignin inhibitors showed a high value of corrosion rate at
the middle rack as compared to the elbow and the end of the rack. A metal sample in EG inhibitor shows the same trend as a sample in
NaCl alone.
The decrease in corrosion rate is due to the ability of the inhibitor to retard corrosion attack. The inhibition happened as a result
of the formation of a strong protective layer on the steel surface. The inhibitor of RSE which has a large structure of molecule chains
and less soluble in a corrosive medium of NaCl tend to form ferric complex-extract. This metallic-organic compound was able to
adsorb on the surface. The metal-adsorbate complexes which have a low solubility rate not only have strong adsorption efficiency but
also effectively inhibit corrosion [36]. An inhibitor will reduce a corrosion effect on the metal surface by forming an inhibitor film or
by adsorbing on to the sand surface, thus decelerate and alter the impact of sand movement [37].
Fig. 10 shows the results of corrosion inhibition efficiency calculated based on analysis of weight loss data. RSE exhibited re-
spectable efficiency with 61, 75 and 83% of the steel positioned in the middle, elbow and end of rack respectively. Lignin shows 20,
61 and 72% efficiency at each different steel positions. Meanwhile, EG shows the lowest inhibition efficiency at all the three posi-
tioned samples; 20, 26 and 43% correspond to middle, elbow and end. All types of inhibitors exhibit good corrosion inhibitive impact
at the end of the rack. The order of corrosion severity in test rack was; end > elbow > middle for both NaCl alone and EG. Mean-
while, in the presence of RSE and lignin, corrosion severity acts differently; middle > elbow > end.
The difference in the order of corrosion severity is due to the different dynamic contact of inhibitor solution. A solution agitation
at the end of the rack was more turbulent and provide a large contact for inhibition. The inhibitor molecules capable of joining oxide-
hydroxide compound to form a protective layer on the steel surface. The molecular concentration of a combined optimum corrosion
inhibitor with corrosion products provides an excellent inhibition efficiency of erosion-corrosion [37]. The resulting oxide on the
metal surface helps to retard corrosion. High inhibition efficiency as shown by RSE reflected the association of optimum inhibitor
with a sand particle or corrosion products which have been accumulated at the end of the rack. Consequently, the formed protective

Fig. 8. Solution flow directions in corrosion test rack, (a) laminar, (b) turbulent, (c) impingement.

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Table 4
Morphology of steel surface at different positions in the corrosion test rack after exposed with 3.5% NaCl solution at 30 °C.
MIDDLE END ELBOW

Image of the metal specimen

after exposed in 3.5% NaCl

Irregular and wide shapes Irregular shapes of Spherical shapes of pitting.

of hemispherical pitting. hemispherical pitting.
Combined spherical shape.
Distinctly visible pits/cavity
Region 1

Localized small pits. Localized pits and big Cavity: elongated/chain pits.
cavity.
Invisible pits/cavity
Region 2

Elongated/chain shapes of Big cavity at the edge of the Small cavity at the edge of
pitting at the edge of the sample. the sample.
sample.
Edge of sample
Region 3

(continued on next page)

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Table 4 (continued)

Corrosion products Corrosion products Corrosion products

(oxides); Coral-like (oxides); Coral-like (oxides); Coral-like structure.
structure. structure.

Most severe part of corrosion attack

Region 4

Erosion pattern; wave-like Erosion pattern; cloud-like Erosion pattern; bubble-like

structure structure structure
Mild part of corrosion attack
Region 5

layer protects the high intensity of turbulent flow and reduce the impact of corrosion attack. The growth of oxide layer has changes
the pattern of the dynamic movement of the solution. These results were in agreement with a study of mild steel corrosion in a
carbonate-bicarbonate buffer [38]. The corrosion components and surfaces roughness were reduced by the inhibitors which dom-
inantly adsorbed on the steel surface. Simultaneously, the corrosion product decreased the local turbulent intensity and reduce the
amount of erosion products.

Fig. 9. Corrosion rate of uninhibited and inhibited steel in NaCl, RSE, lignin and ethylene glycol (EG) at a different position in the corrosion rack.

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Fig. 10. Corrosion inhibition efficiency of steel in three types of corrosion inhibitors at a different position in corrosion rack.

3.4. Observation on uninhibited and inhibited steel surface in 3.5% NaCl and CI flow at 40 °C

Fig. 11 shows the image of steel specimens in NaCl solution captured by the high-resolution optical camera. Four images represent
four pieces of coupon placed in the same position for the purpose of data replication. The morphology of uninhibited steel in NaCl
solution shows uniform corrosion with tiny pits over the whole steel surface. Image of steel in the middle of the rack (Fig. 11a1–a4)
shows less corrosion degradation compared to the others. This is because the specimen experienced laminar flow which provides less
blow impact with uniform stream and minimum contact. It is observed that the distribution of localized pores was unidentical and
showed striped-structure.
Meanwhile, pits and rough structure on the specimen at the end of the rack (Fig. 11b1–b4) were found to be uniform and evenly
distributed over the whole surface. This results from the turbulence effect at the end of the rack wherever NaCl solution agitated and
hit the inner wall of the steel surface. The movement of NaCl ions provided high intense and large contact. A study on the effect of
turbulent at various velocities revealed the production of localized corrosion on a surface due to the increase in electrostatically
inhibitors removal prior to change in current potential [32]. The rough surface of the specimen would be the factors of increased in
ion transportation by high turbulence levels [39], though increased the erosion-corrosion. Corrosion of steel in the elbow of the rack
(Fig. 11c1–c4) shows the corrugated pore shape which definitely affected by the direction and dynamic of the solution. The rolling
flow of NaCl ions in the elbow space cause the steel surface form pitting and remained the scratches texture. The erosion-corrosion in
the elbow of pipe was increased resulted from the roughening of the metal surface because erosion is sensitive to the impingement
angle of solid particles [40].

Fig. 11. Image of steel surface in 3.5% NaCl at 40 °C at different positions of specimen in corrosion rack; middle (a1–a4), end (b1–b4), elbow (c1–c4).

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Fig. 12. Image of steel surface in RSE at different positions of the specimen in corrosion rack; middle (a1–a4), end (b1–b4), elbow (c1–c4).

Fig. 12 shows the effect of RSE as corrosion inhibitors for steel in NaCl. The steel shows very less corrosion damage and a
minimum localizes pits. Both characters were shown by almost all the samples at all positioned specimen. A specimen at the end of
the rack shows respectable corrosion protection.
Fig. 13 shows the results of steel in lignin inhibitor. The steel surface shows serious corrosion attack with visible large pits and
cavities almost on the entire steel surface mainly in the middle of the rack (Fig. 13a1–a4). This result reflected the high value of
corrosion rate. It is suggested that the inhibitors film was prohibited to form due to the local acidification in the erosion pits,
inconsequence corrosion rate increased [41] and inhibition efficiency decreased. While the steel at the end (Fig. 13b1–b4) and elbow
of the rack (Fig. 13c1–c4) show localized pitting with uneven distribution which is less severe compared to steel in the middle of the
rack.
Fig. 14 shows the effect of steel corrosion in EG inhibitors. A steel in the middle of the rack (Fig. 14a1–a4) shows less corrosion
attack compared to others position. The distribution of pore and pits remained uneven and scattered over the surface. The specimen
surface shows a pattern such a line texture of laminar flow. The effect of corrosion attack on a specimen in the end (Fig. 14c1–c4) and
elbow (Fig. 14c1–c4) of rack gives an almost similar appearance. The steel surface was found to be corroded at a certain part of steel.
However, referring to the graph in Fig. 9, a specimen at the end of rack gives high corrosion rate values compared to the specimen in
the elbow of the rack. This means that the EG inhibitor performed low efficiency to retard steel corrosion at the end of the rack. The
high impact of the corrosion products onto the steel surface resulted in the erosion-corrosion at the end of the rack. Therefore,
corrosion product which initially facilitated in protecting the surface was broken off due to the continuous flow of inhibitors. In
addition, the weak adsorption of EG molecules prior to the formation of corrosion product on the surfaces also being the factors of
severe corrosion attack. The high velocity of fluid tends to remove the inhibitor films from the metal surface and decreased the
inhibition efficiency [42–45]. Dissolution of metal that occurs in high rate, will slow down the inhibitors adsorption process. This
phenomenon explained by the electromechanical inhibitor resorption model by assuming that when the substrate metal atom goes
into solution, inhibitor molecules are desorbed [46].

3.5. Observation of sample via SPM

Fig. 15 shows the topography image of steel surface at the end of rack obtained via SPM. A bare metal (Fig. 15a) shows a smooth
surface represents a specimen without immersion. A steel in NaCl alone (Fig. 15b) exhibits a rough an uneven texture indicating both
dissolutions of metals and oxide film. It is noted that the maximum height scales reached up to 300 nm for the specimen in NaCl alone
compared to others. The rough structure of the surface was found to be different from the sample treated in corrosion inhibitors. A
specimen in NaCl alone and EG shows subtle rough texture, while inhibited specimens in RSE (Fig. 15c) and lignin (Fig. 15d) shows a
large rough texture with a reduction in a maximum height scales. It is suggested that the large rough texture resulted from the slow
rate of metal dissolution due to corrosion inhibition.
Table 5 represents the value of surface roughness Ra of the specimen according to the quantification of roughness on scanned
surfaces via SPM. The steel in NaCl alone shows the highest roughness value up to 31.844 μm. The roughness of the specimen was
decreased, particularly for steel in RSE solution which shows the lowest, 18.526 μm.
The exposure of steel in the rack containing NaCl and in the presence of corrosion inhibitors has shown the different structure of
corrosion attack in varying corrosion inhibitors. Table 6 shows the proposed illustration of corrosion structure formed on the steel

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Fig. 13. Image of steel surface in lignin at different positions of the specimen in corrosion rack; middle (a1–a4), end (b1–b4), elbow (c1–c4).

surface (side view) at all positions in the rack. This proposed illustration was adapted from all the results obtained from the surface
analysis.
Steel surfaces exposed to the flow of NaCl solution without corrosion inhibitor has suffered serious pitting corrosion and even-
tually form general or uniform corrosion. General corrosion has destroyed almost the entire surface of the steel through a metal
dissolution process. Thus, the size was reduced resulting in high weight loss and severe roughness. Steel in the inhibitors of the RSE
showed slight effects of pitting corrosion. RSE has inhibited the formation of pits and prevent general corrosion over the whole
surface. Steel exposed in the lignin inhibitors demonstrated a moderate effect of pitting corrosion. Meanwhile, specimen in EG
inhibitor exhibits a large area of pitting corrosion. The continuous exposure and flow of EG solution caused the development of
localized pores. Consequently, led to the establishment of uniform pores and pits on the overall of steel surface. The corrosion of steel
in EG inhibitor experienced the erosion-corrosion, indicated by the wide area of corrosion attack.
In the chemistry aspect, the effectiveness of all the three inhibitors used can be assessed through the molecular structure. A major
compound in RSE has a large molecule configuration. For example, 4-Allylsyringol have two functional groups of methoxy (–OCH3)

Fig. 14. Image of steel surface in EG at different positions of the specimen in corrosion rack; middle (a1–a4), end (b1–b4), elbow (c1–c4).

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Fig. 15. Image of steel surface at the end of rack (a) bare metal (b)NaCl solution (c) RSE. (d) Lignin (e) EG.

and one functional group of hydroxyl (–OH) surrounding the aromatic benzene ring (Fig. 4b). Both functional groups are known as
electron donating groups which are the fundamental characteristic of good inhibitors selection [47–49]. This kind of configuration
provides more chances for RSE to broadly cover on the metal surfaces for interaction, thus inhibit corrosion. The double –OCH3 group
and the single –OH occupied on the benzene ring will provide more electron density in the structure. Meanwhile, a molecule structure
of coniferyl alcohol (Fig. 5), a major compound in lignin has a single group of –OCH3 attached to a benzene ring. This structure
relatively small and have limited space for adsorption. A less electron density surrounds the chemical structure offers low capability
in inhibition interaction. For ethylene glycol (Fig. 6), although the double –OH groups were present in the structure, the inhibition
efficiency was still lower than other studied inhibitors. The chemical structure is unfavourable for broad interaction within metal's

Table 5
Roughness values for steel specimen obtained via SPM.
Specimen Roughness, Ra(μm)

Bare steel 6.912

Steel in NaCl 31.844
Steel in RSE 18.526
Steel in lignin 20.424
Steel in EG 22.121

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Table 6
Proposed illustration of corrosion structure on steel (side view) without and with corrosion inhibitors.
Steel condition Steel structure Condition

Bare steel No corrosion

Steel in NaCl Erosion, pitting and general

corrosion

Steel in RSE Very less pitting corrosion

Steel in lignin Moderate pitting corrosion

Steel in EG Severe pitting corrosion,

approaching general corrosion,
erosion corrosion

active site due to the short aliphatic chain. Varieties of functional groups in a number of lignin compounds were the factors of low
inhibition due to the competitive interaction among electrons and structures configuration.

3.6. Mechanism of inhibition

Through all the findings and discussion above, the mechanism of corrosion inhibition of steel in the multiple flow loop under
3.5% NaCl in the presence of RSE can be simplified in three ways:

3.6.1. Replacement of adsorbed water molecule

Generally, the organic inhibitor (Org) will react on a metal surface by replacing the formerly adsorbed water molecule as ex-
plained by the Eq. (3) [1] resulting in the formation of a protective film on the steel surface. In the equation, aqueous and adsorbed
phases were represented as “aq” and “ads” respectively, meanwhile n is referred to the number of water molecules which must be
desorbed to permit the accommodation of inhibitor on the steel surface. The protective film provides a barrier for further steel
dissolution thus inhibit corrosion. In our studies we believed the interaction within RSE and metal surface could happen similarly too
and as withdrawn in Eq. (4). As RSE inhibitors were introduced in an electrolyte, the inhibitors molecules will orientate and co-
ordinated towards the active site for adsorption by replacement of water molecule.

Fig. 16. A schematic representation for adsorption mode of major RSE compound on steel surface.

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S. Yahya, et al. Engineering Failure Analysis 100 (2019) 365–380

Org (aq) + nH2O (ads) Org (ads) + nH2O (3)

RSE (aq) + Fe/(nH 2O) ads (Fe / RSE ) ads + nH 2O (aq) (4)

3.6.2. Two characters of the adsorptive mode

The occupied RSE molecules have two possibilities of adsorptive mode either can strongly remain to adsorb on surface by
chemisorption; interaction between (a) unshared electron pairs of heteroatoms O or (b) pi-electrons of aromatic rings with vacant d-
orbital of surface Fe atoms, or weakly adsorb by physisorption; (c) electrostatic interaction between positively charge RSE and already
adsorbed chloride ions. For example, the major compound in RSE which is 4-Allylsyringol is able to perform adsorption as shown in
Fig. 16. This character was dependent on the varieties of the compound, molecule structure presence in RSE and ionic species in the
electrolyte. A different molecule compound with the different functional group or active site will give different capabilities in the
inhibition effect.

3.6.3. Formation of complex

The exposed metallic surface towards the continuous flowing fluid will generate a corrosion product. Inhibitor molecule may
associate with corrosion product by forming a chelating complex with the metal ion and adsorb on the active site. The hydrodynamic
condition may increase the mass transport of insoluble complex, thus properly attach on a rough surface, penetrate into a pit or clog
the pores to inhibit corrosion. The following Eqs. (5)–(8) may explain the path of corrosion inhibition [5,10,50,51].
Fe Fe2 + + 2e (5)

1 O + H O + 2e
2 2 2 2 OH (6)

Fe 2 + + 2 OH Fe (OH ) 2 (7)

[Fe (OH )] ads + RSE [Fe (OH )/ RSE ] ads (8)

The reaction begins with the dissolution of steel and oxygen reduction in near neutral NaCl, followed by formation of typical
corrosion product, ferrous hydroxide Fe(OH)2, and end up with association and adsorption of RSE inhibitors molecules with corrosion
products to become an adsorbed insoluble complex on the metal surface.
The reaction rate of corrosion inhibition was strongly dependent on the temperature, concentration of inhibitors, exposure time
and flow rate of the inhibitors systems.

4. Conclusion

The inspection of steel corrosion in a multiple flow loop simulated via corrosion test rack has been successfully done. The findings
are concluded as follows:

• A steel surface exposed in 30 °C of NaCl at different positions in multiple flow loop shows varieties in the configuration of
corrosion attack as viewed through the high-resolution microscopic analyser. The difference in corrosion damage resulted from
the different fluid flows; laminar, impingement and turbulent. The steel surface showed slight damage with the growth of oxide as
compared to exposure in 40 °C of the solution.
• A steel exposed in 40 °C of NaCl with and without inhibitors showed dissimilar patterns of corrosion damage at different posi-
tioned specimen as viewed through a high-resolution optical camera and SPM. The steel at the end of the rack exhibited very less
corrosion effect whenever exposed to RSE inhibitors.
• The order of corrosion severity of the steel in the test rack in NaCl alone and in the presence of EG was; end > elbow > middle.
Whereas, the order of corrosion severity of the steel in RSE and lignin inhibitors was; middle > elbow > end of the rack.
• SPM analysis revealed the roughness of steel surface reduced with the application of the RSE. RSE inhibitors were able to maintain
the steel structure and shape compared to lignin and EG.
• The order of the best performance of corrosion inhibitor efficiency was; RSE > Lignin > EG. The efficiency was dependent on the
chemical structure, composition of compounds and the existence of functional groups.

A few thoughts on future research for improvement are as follows:

• The other complex variables such as types of brine water, pH, flow rate, temperature, pressure and contact time should be further
study by using Response Surface Methodology (RSM) to design the experiments for optimum results.
• The involvement of microbe in the fluid system will represent a good simulation for real condition in the pipeline.
• The use of various metals, types, sizes and dimension will provide a better understanding of corrosion configuration in the
multiple flow loop at different flow regime.
• A deep analysis in term of morphological studies such as Scanning Electron Microscopy-Electron Diffraction Spectroscopy (SEM-
EDS), X-ray Diffractometry (XRD), and mapping the corrosion pattern is required for interpreting the corrosion mechanistic.

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Acknowledgment

The authors would like to thank the Ministry of Science, Technology & Innovation, Malaysia (MOSTI) for the financial support
given through the Sciencefund Grant Scheme (03-01-02-SF0734). S.Yahya would like to thank the Ministry of Higher Education,
Malaysia (MOHE) with their support through MyBrain15 (MyPhD) scholarship. Authors also would like to thank editor and reviewers
in their suggestion and comments to improve the quality of this manuscript.

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