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Accepted Manuscript

Title: Study of pitting corrosion of L245 steel in H2 S


environments induced by imidazoline quaternary ammonium
salts

Author: Peng Han Changfeng Chen Haobo Yu Yizhen Xu


Yanjun Zheng

PII: S0010-938X(16)30299-2
DOI: http://dx.doi.org/doi:10.1016/j.corsci.2016.07.006
Reference: CS 6835

To appear in:

Received date: 12-2-2016


Revised date: 8-7-2016
Accepted date: 8-7-2016

Please cite this article as: Peng Han, Changfeng Chen, Haobo Yu, Yizhen
Xu, Yanjun Zheng, Study of pitting corrosion of L245 steel in H2S
environments induced by imidazoline quaternary ammonium salts, Corrosion Science
http://dx.doi.org/10.1016/j.corsci.2016.07.006

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Study of pitting corrosion of L245 steel in H2S environments induced by
imidazoline quaternary ammonium salts
Peng Han a, b, Changfeng Chen a, b*, Haobo Yu a, b, Yizhen Xu a, b, Yanjun Zheng a, b
a
Department of Materials Science and Engineering, b Beijing Key Laboratory of Failure, Corrosion and Protection
of Oil/gas Facilities, China University of Petroleum (Beijing), 18 Fuxue Road, Changping District, Beijing 102249,
P. R. China

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Highlights
L245 steel suffered severe pitting corrosion only when IM inhibitor was added.

NaCl accumulated on local L245 steel surface area and it forms galvanic

corrosion system with surrounding area.

The surface potential of NaCl accumulated area is low and pitting corrosion occur

in this area.

The extent of pitting corrosion on L245 steel decreased with increasing IM

inhibitor concentration.

The pitting corrosion was inhibited by IM+OP inhibitor.

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Abstract: The corrosion characteristics of L245 steel were analyzed under H2S
atmosphere in stratum water with imidazoline quaternary ammonium salt (IM), and
IM mixed with octylphenol polyoxyethene ether (OP). L245 suffered pitting corrosion
in solutions with only IM, but pitting corrosion was inhibited in solutions with IM and
OP. Local damages of the adsorbed IM film appeared on the steel surface in solutions
with only IM. While Cl- accumulated on these areas, surface potentials were lower
than surrounding areas, and a small anode/large cathode galvanic corrosion system
was formed. The influence of inhibitor on pitting corrosion for L245 steel was
discussed.
Key words: A. Carbon steel; B. Weight loss; B. AFM; C. Acid corrosion; C. Acid

inhibition

3
1. Introduction

Pipeline steels used in the oil and gas industry suffer severe H2S corrosion [1-4].

Inhibitor injection is standard practice to control the corrosion [5-13], attributed to

inhibitor adsorption forming a protective film layer [14-16].

However, a few reports have shown that sometimes the addition of inhibitor

induces pitting corrosion of metals. Ngala found that pitting corrosion occurred on

reinforced concrete specimens in non-carbonated concrete with high Cl- levels or

carbonated concrete with low Cl- levels, even though calcium nitrite inhibitor was

introduced [17]. Similarly, Diaz found the corrosion efficiency of carboxyethyl

imidazoline decreased over time, and pitting corrosion was observed on carbon steel

under H2S environment in solution containing 10 vol% diesel, accelerating corrosion

of the metal [18].

Although the exact mechanism of pit initiation remains uncertain, three main

mechanisms: penetration [19,20], film thinning [21] and film rupture [22], have been

proposed to explain pitting corrosion. Pit initiation is usually due to local breakdown

of passive or protective film [23,24]. Since the inhibitor can adsorb on metal surfaces,

forming a film layer, Garcia considered that pitting corrosion of carbon steel was

attributed to pores in the adsorbed hydroxyethyl imidazoline layer [25]. Helena

suggested that the porosity of the adsorbed imidazoline film increased with immersion

time and finally local corrosion occurred on the metal surface [26]. Regardless of the

subsequent mechanism, it is clear that pit initiation in the presence of inhibitor is

related to the adsorbed inhibitor film layer.

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Pitting corrosion can be divided into two stages: pit initiation and growing.

However, pit growing, induced by inhibitor, has not been discussed elsewhere.

Imidazoline derivatives are effective inhibitors, with excellent inhibition

performance and environmental friendliness, and have become widely used [27-34].

However, we found that L245 steel suffered pitting corrosion induced by imidazoline

quaternary ammonium salt (IM) in H2S environment. The uniformity of the adsorbed

inhibitor film was analyzed using scanning kelvin probe force microscopy (SKPFM)

and electrochemical noise techniques, and the influence of inhibitor on pitting

corrosion of L245 steel was illuminated and discussed.

2. Experimental method

2.1 Material preparation

Analytical grade octylphenol polyoxyethene ether (OP) (Fig. 1(a)) was used. IM

(Fig. 1(b)) was synthesized from analytical grade oleic acid, diethylenetriamine, and

benzyl chloride. The synthetic route to IM is shown in Fig. 2. Oleic acid and

diethylenetriamine (molar ratio 1:1) were added to a round bottomed flask equipped

with a reflux system and mechanical stirring. The solution reaction initially proceeded

for 3 h at 140 C, and then the reaction temperature was raised to 180 C for 4 h, and

raised again to 260 C for 3 h, yielding a light yellow liquid: product I. Benzyl

chloride was added to and fully reacted with product I at 75 C (molar ratio 1:1).

Solvent was removed by drying in a vacuum oven, yielding a light brown liquid:

product II (IM). The yield of IM was 93.8 %. The structure of IM was verified by

infrared spectrum (IR) and 1H NMR. IR(KBr, cm-1): 3240 cm-1 (N-H), 2928 cm-1

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(C-H), 2849 cm-1 (C-N), 1615 cm-1 (C=N), 693 cm-1 (N-H). 1H NMR (Bruker AV600

MHz spectrometer, Acetone): chemical shifts d (ppm): 0.88 (t, 3H, (CH3)), 1.11 (m,

8H, -(CH2)4), 1.31 (m, 18H, (CH2)9), 1.59 (s, 2H, -C-NH2), 2.07 (m, 2H,-CH2-N),

2.60 (m, 4H, (=C-CH2)2), 3.50 (m, 6H, (N+-CH2-C)3), 5.30 (m, 2H, (CH=CH)), 7.30

(m, 5H, C6H5). IM+OP is a mixture of IM (80 wt%) and OP (20 wt%).

L245 steel with chemical composition (wt%) C (0.13%), Mn (0.76%), S (0.014%),

P (0.022%), Si (0.24%) and Fe (balance) was used. Sample dimensions 50mm

10mm 3 mm were cut from L245 stock for weight loss measurements. Columned

samples 12 5 mm were cut for electrochemical and SKPFM measurements. Prior

to each experiment, the working electrode was mechanically abraded with emery

paper beginning from 400 # to 2000 #, then polished with diamond abrasive (0.5 m)

to a mirror face, rinsed with double distilled water and dried in air.

2.2 Weight loss tests

Weight loss measurements were performed in wide mouthed jars at 75 C.

Stratum water consisting of NaCl (1.119 g L-1), KCl (0.045 g L-1), CaCl2 (3.003 g

L-1), MgCl2 (1.191 g L-1), NaHCO3 (0.417 g L-1), Na2SO4 (0.102 g L-1) was used as

test solution.

Three specimens were immersed in the test solution without inhibitor and with the

addition of 90 mg L-1 IM, 180 mg L-1 IM, 360 mg L-1 IM, 90 mg L-1 IM+OP, 180 mg

L-1 IM+OP and 360 mg L-1 IM+OP inhibitor. The solutions were deoxidized using

high purity N2 (99.999%) for 2 h. After that, H2S gas was pumped into the solution

continuously. After immersion for 168 h, samples were rinsed with double distilled

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water and dried in air. Sample surfaces were inspected using scanning electron

microscope (SEM, Quanta 200F field, FEI Inc.). Corrosion rates and inhibition

efficiencies were determined following methods reported in detail elsewhere [3538].

Standard deviations were calculated from 3 identical measurements

2.3 Electrochemical test

2.3.1 Open circuit potential and potentiodynamic polarization tests

Electrochemical measurements were performed in a conventional three-electrode

cell, using CHI660-E electrochemical workstation. L245 steel was used as the

working electrode (WE), graphite rods as the counter electrodes, and saturated

calomel electrode (SCE) with Luggin capillary salt bridge as the reference electrode.

The stratum water consists of NaCl (1.119 g L-1), KCl (0.045 g L-1), CaCl2 (3.003 g

L-1), MgCl2 (1.191 g L-1), NaHCO3 (0.417 g L-1), Na2SO4 (0.102 g L-1) was used as

test solution. Before each tests, the test solution was bubbled with N2 (99.999%) for 2

h. Then 45 mg L-1 IM, 90 mg L-1 IM, 180 mg L-1 IM, 360 mg L-1 IM, 45 mg L-1

IM+OP, 90 mg L-1 IM+OP, 180 mg L-1 IM+OP and 360 mg L-1 IM+OP inhibitor was

added in the test solution, respectively. H2S (99.99%) gas was introduced into the test

solution and the open circuit potential (OCP) was recorded for 30 min until a stable

state reached (OCP fluctuation less than 5 mV vs. SCE) [13]. Potentiodynamic

polarization tests were performed by polarization from -1.0 to - 0.3 V vs. SCE with a

scan rate of 1 mV s-1. Three or four measurements were performed for each

experimental condition to estimate repeatability, with a relative standard deviation of

less than 5%. All potentials reported here are referenced to SCE. The linear Tafel

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segments of the cathodic curves were extrapolated to the corrosion potential to obtain

the corrosion current density [39], and inhibition efficiency values were obtained

following methods reported in details elsewhere [40,41].

2.3.2 Electrochemical noise tests

Electrochemical noise (EN) was measured using a three electrode system connected

to a CHI660-E workstation. Two L245 electrodes were used as the WE1 and WE2

electrodes and a saturated calomel electrode with Luggin capillary salt bridge as the

reference electrode. 3 wt% NaCl solution was used as test solution, solution pH was

adjusted to 3.0 using analytical grade sulfuric acid. Before each test, the test solution

was bubbled with N2 (99.999%) for 2 h, then 90 mg L-1 IM inhibitor and 90 mg L-1

IM+OP inhibitor was added to the test solution. L245 steel was immersed in the test

solution for 24 h, and then the potential and current curves of L245 steel were

recorded. The test frequency was 4 Hz. To avoid external signal interference, all EN

measurements were completed in a Faraday shielding box. The influence of large

distortions in the processing of noise was mitigated by removal of the DC trend

applied over an average baseline, as previously established by Tan et al. [42].

2.4 Scanning kelvin probe force microscopy tests

The test solution was 3 wt% NaCl solution. Before each test, the test solution was

bubbled with N2 (99.999%) for 2 h, then electrodes were immersed in the test solution

in the absence and presence of 90 mg L-1 IM and 90 mg L-1 IM+OP for 30 s. The

samples were removed from the solution holding the immersed surfaces facing

downwards. Solution left on the surface was absorbed using filter paper and dried in

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N2 atmosphere. The prepared sample surfaces were first observed using scanning

electron microscope (SEM, Quanta 200F field, FEI Inc.). Then the surface

morphology and surface potential was measured using Scanning kelvin probe force

microscopy (SKPFM) in an atomic force microscope (Nanoscope III, Veeco

Instruments Inc.). SKPFM tests were performed at room temperature with the samples

in air. SCM-PIT plated PtIr Nanoprobe (60100 kHz) was used, pixel density was 512

512 and scan rate was 0.1 Hz.

3. Results

3.1 Open circuit potential and potentiodynamic polarization analysis

The open circuit potential and potentiodynamic polarization curves for L245 steel

in stratum water saturated with H2S, stratum water with various concentrations of IM,

and stratum water with various concentrations of IM+OP were measured at 75 C.

The results are displayed in Fig. 3. Corrosion potential increase in the presence of IM

or IM+OP inhibitor, and anodic polarization current density decreases significantly.

Thus, IM and IM+OP inhibitors worked as mixed-type inhibitors with predominantly

control of anodic reactions [13]. The anodic polarization current density increased

rapidly when anodic polarization potential was approximately 300 mV vs. SCE

greater than the corrosion potential. This indicates that adsorbed inhibitor molecules

desorbed from the L245 surface in this situation, which reduced the ability of inhibitor

molecules to protect the metal substrate from corrosion [43]. Furthermore, the IM+OP

inhibitor desorbed at higher polarization potential than solutions including only IM

inhibitor. Thus, adsorption of IM+OP molecules onto L245 steel surface is more

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stable than IM molecules.

Fig. 4 shows corrosion current densities and inhibition efficiencies of L245 steel in

the absence of inhibitor, and in the presence of various concentrations of IM and

IM+OP inhibitors. Inhibition efficiency increased with inhibitor concentration, but the

inhibition efficiency of IM+OP in stratum water was higher than that observed with

IM at the same concentration. This observation indicates that IM+OP displays better

inhibition efficiency than IM.

3.2 Weight loss analysis

The corrosion rates of L245 steel by weight loss test in stratum water saturated with

H2S, stratum water with various concentrations (90 mg L-1 to 360 mg L-1) of IM,

stratum water with various concentrations (90 mg L-1 to 360 mg L-1) of IM+OP were

measured at 75 C. The results are displayed in Fig. 5(a). L245 steel suffered severe

corrosion in the solution without inhibitor, compared to solutions including inhibitors.

After the addition of inhibitor, the corrosion rate of L245 steel decreased greatly.

Indeed, the corrosion rate of L245 steel in stratum water with IM+OP inhibitor is less

than that observed in stratum water with IM under the same experimental conditions

(Fig. 5(a)), while IM+OP shows higher inhibition efficiency than IM (Fig. 5(b)). The

inhibition efficiencies show the same trend as that observed for the electrochemical

tests.

The micro-morphologies of the corroded surfaces of L245 steel are shown in Fig. 6.

It shows that, after immersion in the solution without inhibitor, a layer of corrosion

scale formed on the L245 steel surface (Fig. 6(a)). This is because the dissolved H2S

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was ionized in the solution, which generated HS- and S2-. Fe2+ was formed during the

anode reaction, which combined with S2- at the metal/solution interface, resulting in a

layer of corrosion scale (FeS) being deposited on L245 steel surface [44,45]. The

corrosion scale may protect the metal surface from corrosion to some extent, but local

breakdown of the corrosion scale may cause pitting corrosion [46,47]. The corrosion

scale is homogeneous, and the entire surface shows general corrosion.

However, after immersion in a solution to which 90 mg L-1 IM have been added,

severe pitting corrosion is observed on the surface of L245 steel (Fig. 6(b)). The

maximum pitting corrosion rate is approximately 52.1 mm y-1. There was no

significant corrosion scale cover on the surface of L245 steel, but some corrosion

scale accumulated at the entrance of the corrosion pit. Visual inspection suggested the

pit had developed into a deep hole, which is confirmed by the cross-section view (Fig.

6(c)). The pit shows a typical pitting corrosion feature, that is, the entrance of the pit

is small whereas the bottom is rather large. No corrosion products were found inside

the pit. After immersion in a 180 mg L-1 IM solution and in a 360 mg L-1 IM solution,

pitting corrosions are observed on L245 steel surfaces (Fig. 6(e) and (Fig. 6(g)).

Moreover, the corrosion pit sizes decreased with increasing inhibitor concentration, in

other words, the extent of pitting corrosion decreased with increasing IM inhibitor

concentration.

After immersion in the IM+OP solution (Fig. 6(d), Fig. 6(f) and (Fig. 6(h)), no

obvious corrosion scale formed on the L245 surface, nor did pitting corrosion occur,

L245 steel surface showed some general corrosion features.

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3.3 Electrochemical noise measurements

As the initiation of corrosion pits on metal surfaces is always associated with

transient fluctuations in the potential and current curves, the electrochemical noise

method can be used to record these disturbances and thus to capture the nucleation

and growth signals of pits [48-53].

The potential and current plots recorded on L245 steel in 3 wt% NaCl solution

without inhibitor, 3 wt% NaCl solution with 90 mg L-1 IM, and 3 wt% NaCl solution

with 90 mg L-1 IM+OP were dealt with DC trend removal, results are displayed in Fig.

7. These show that the amplitude of current fluctuations recorded on L245 steel in the

test solution without inhibitor is about 0.02 A, while the amplitude of potential

fluctuations recorded on L245 steel is about 25 mV vs. SCE (Fig. 7(a)). The sharp

fluctuations are absent, as is common for general corrosion of metals [54,55].

In contrast, in the 90 mg L-1 IM solution, sharp fluctuations occur in both the

current and potential curves recorded on L245 steel (Fig. 7(b)). In other words, during

these fluctuations, current suddenly appears to surge while potential suddenly appears

to decrease. Researchers generally believe that these sharp fluctuations of current and

potential are caused by breakdown and repair of the protective film on the metal

surface [56-58]. This is the common character of pitting corrosion of metals.

IM is an adsorption-type corrosion inhibitor that can adsorb on metal surfaces and

thus inhibit dissolution of the metal. Fig. 7(b) shows local breakdown and repair in the

adsorbed IM film layer. Local breakdown of the inhibitor film results in an increase of

current density, and re-adsorption of inhibitor can inhibit the corrosion of L245 steel.

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Thus, sharp fluctuations in both the potential and current curves occur.

In the solution to which 90 mg L-1 IM+OP has been added, the amplitude of current

fluctuations recorded on L245 steel is about 0.01 A, the amplitude of potential

fluctuations recorded on L245 steel is about 16 mV vs. SCE (Fig. 7(c)). No sharp

fluctuations occur in both the potential and current curves. The electrochemical noise

results exhibit similar characteristics as are observed in the uninhibited solution. The

observations show that L245 steel suffered some general corrosion. This also

demonstrates that local breakdown phenomena do not readily occur when IM+OP was

adsorbed onto the metal surface.

3.4 Scanning kelvin probe force microscopy tests

Adsorbed inhibitor molecules on a metal surface form a film layer, which changes

the work function of the metal surface [59,60]. SKPFM method can be used to

measure the change in work function, which reflects the adsorption state of the

inhibitor on the metal surface [61].

After immersion of the samples in 3 wt% NaCl solution without inhibitor, 3 wt%

NaCl solution with 90 mg L-1 IM inhibitor, and 3 wt% NaCl solution with 90 mg L-1

IM+OP inhibitor, the dried surfaces of L245 steel were examined by means of SEM.

It is apparent that some isolated NaCl particles, which are square in shape, are

distributed on the sample surface (Fig. 8).

In compare with the morphologies observed in Fig. 8, the surfaces at a higher

magnification was observed, the mapping images of L245 steel surfaces after

immersion in solutions with IM and IM+OP were recorded at the same time, where Cl,

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Na, N and O are identified, results are displayed in Fig. 9. As it shows, after

immersion in solution with IM inhibitor (Fig. 9(a)), local Cl and Na accumulated

areas appear, while the distribution of N element from mapping images and EDX

results on L245 steel after immersion in IM solution is not that dramatic, this probably

dues to the thin layer of adsorbed inhibitors film on L245 steel surface. By contrast,

the distribution of Cl and Na on L245 steel surface is homogeneous after immersion

in solution with IM+OP inhibitor (Fig. 9(b)).

Surface morphologies obtained using SKPFM show that after immersion in 3 wt%

NaCl solution and dries in a N2 atmosphere (Fig. 10(a)), a continuous layer of

nanoscale NaCl particles covered the surface of the sample and the distribution of

these NaCl particles are homogeneous. The formation of these nanoscale particles

may be related to the adsorption of a thin liquid film on the metal surface [62,63].

However, after immersion in 3 wt% NaCl solution with 90 mg L-1 IM inhibitor, local

accumulations of NaCl appear (as shown in the blue circle in Fig. 10(b)). The

phenomenon is consistent with that observed in Fig. 8. The sizes of these areas are

about 1.9 m, the NaCl particles in these areas are larger than in the surrounding areas,

and they are packed closely together. This observation suggests that in the 3 wt%

NaCl solution with 90 mg L-1 IM, the adsorption of IM molecules on metal surface is

non-homogeneous. However, after L245 steel immersion in 3 wt% NaCl solution with

90 mg L-1 IM+OP inhibitor, the deposit nanoscale NaCl particles on the surface show

the homogeneous feature. This demonstrates that the adsorption of inhibitor

molecules on the metal surface is homogeneous. According to Zhao et al. [64], mixed

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inhibitor show better synergistic effect. Owing to their interactions with metal surface,

the coverage of the metal surface by inhibitor molecules increased [65-67].

SKPFM was used to measure the surface potential of the samples after drying

under an N2 atmosphere. The results showed that after immersion in the 3 wt% NaCl

solution, the surface potential of L245 steel is homogeneous, as shown in Fig. 10(d).

The green line in Fig. 10(d) is the line analysis position along which the surface

potential was recorded. The surface potential fluctuated between -250 and 250 mV

(Fig. 10(g)). Comparing surface morphology and potential diagram, the surface

potential in the areas where NaCl particles appear was lower and the surface potential

is higher than where no NaCl particles occurred.

After immersion in the test solution to which IM has been added, the surface

potential of L245 steel becomes non-homogeneous. The surface potential in the

location where NaCl particles accumulated is significantly lower than the surrounding

area, as can be seen in the area circled blue in Fig. 10(e). Line analysis of the surface

potential shows that the surface potential difference between the area where NaCl has

accumulated and the surrounding area is greater than 1 V, as shown in Fig. 10(h).

After immersion in the 3 wt% NaCl solution with 90 mg L-1 IM+OP, the surface

potential is homogeneous, as shown in Fig. 10(f), and line analysis shows that the

fluctuation of the surface potential has increased, with the fluctuation appearing

among very tiny areas (0.3 m) on L245 steel surface, as shown in Fig. 10(i). The

sizes of the tiny areas mentioned above are the same as that of the nanoscale NaCl

particles, which indicates that the distribution of NaCl particles is homogeneous and

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there are no NaCl particles aggregate and pack on the L245 steel surface. This also

demonstrates that the inhibitor film is homogeneous and intact across the steel surface.

Maximum surface potential is approximately 1200 mV. This is because the work

function of the L245 steel surface was obviously increased by the adsorption of

inhibitor molecules.

Comparing the surface potentials of L245 steels after immersion in IM and IM+OP

solutions, we can also concluded that the adsorption quantities of inhibitor molecules

on metal surface in mixed systems is more huge and the adsorption intensity is more

strong.

4. Discussion

4.1 Pit initiation

It is well known that the initiation of pit formation results from local breakdown of

the protective layer [68,69]. Electrochemical noise results show that sharp potential

and current fluctuations occur after L245 steel is immersed in a 3 wt% NaCl solution

with 90 mg L-1 IM, which demonstrates local desorption and re-adsorption of

inhibitor molecules. Thus, although IM can form a film layer on the L245 surface,

local damage of the inhibitor film is liable to allow pitting corrosion of L245 steel.

Besides, from Fig. 10(b) we can see that local NaCl accumulations area appear on the

L245 surface, the size of this area is about 1.9 m, which meets the critical size for

the stable pitting corrosion. Under these conditions, a galvanic corrosion system with

a small anode and large cathode is readily formed. The surface potential of local NaCl

accumulations area is 1 V lower than that of the surrounding areas (Fig. 10(h)). From

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potentiodynamic polarization results we can see that IM molecules will desorb from

L245 steel surface when the anodic polarization potential is approximately 300 mV vs.

SCE greater than the corrosion potential. Accordingly, we consider that IM molecules

will not stably adsorb on the local small anodic area due to the high anodic

polarization potential. Therefore, the small exposed anodic location in the galvanic

corrosion system dissolves rapidly and stable pitting corrosion occurs.

Moreover, weight loss results shows the extent of pitting corrosion on L245 steel

decreases with increasing IM inhibitor concentration (90 mg L-1 - 360 mg L-1). This is

probably because IM molecules coverage will gradually become homogeneous with

increasing IM inhibitor concentration.

Mixed inhibitor generally exhibits better adsorption homogeneity, higher

adsorption stability, and inhibits the corrosion more effectively. In this paper,

potentiodynamic polarization results confirm that IM+OP exhibits better inhibition

efficiency than IM alone, and the IM+OP inhibitor film adsorption is more stable.

Thus, we consider that the adsorbed IM+OP film on L245 steel does not easily suffer

local damage. In addition, from (Fig. 10(c)) we can see that no local accumulations

areas appear on L245 steel surfaces. Therefore, the adsorbed IM+OP inhibitor

molecules on the surfaces are considered to be homogeneous. As a result, L245 steel

only suffered general corrosion in solutions with IM+OP inhibitor.

4.2 Pit propagation

Pit morphology (Fig. 6(b) and (c)) shows that the corrosion scale formed by the

dissolution of the metal is stacked on top of the pit, with almost no corrosion scale

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deposit inside the pit. The entrance of the pit is small and the bottom of the pit is large,

which is a typical of autocatalytic pitting corrosion in an occluded cell. It is well

known that FeS corrosion scale is formed during the H2S corrosion process. FeS

solubility is low [70], that is, FeS is relatively insoluble in water. The corrosion scale

is found on top of the pit and there is no corrosion scale inside the pit, which indicates

that the acidity inside the pit wass relatively high. Diffusion of Fe2+ from the pit into

the electrolyte was impeded by the accumulation of the corrosion scale on top of the

pit, and hence accumulated inside the pit. Thereupon, Cl- ions subsequently migrated

into the pit from the electrolyte to maintain charge neutrality, combining to form

FeCl2, increasing acidity inside the pit, and further accelerated the dissolution of metal

[71]. In other words, the pit began to expand rapidly.

Since Fe2+ and H+ accumulated in the pit, a concentration cell with the solution

outside of the pit was formed. This favors diffusion of the anion into the pit. However,

the ionized IM molecule carries a positive charge (Fig. 2(b)), and is unable to migrate

into the pit owing to electric field repulsion. Thus the pit expansion cannot be

prevented by the inhibitor.

5. Conclusions

(1) General corrosion appeared on L245 steel surface in H2S saturated stratum water

at 75 C. But L245 steel suffered pitting corrosion under the same conditions as

mentioned above after adding IM inhibitors.

(2) Local damage of the adsorbed IM inhibitor film was liable to appear on the L245

steel surface only in solutions with IM inhibitor, pitting corrosion occurred due to

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the formation of small anode and large cathode galvanic corrosion system.

(3) The extent of pitting corrosion on L245 steel decreased with increasing IM

inhibitor concentration (90 mg L-1360 mg L-1).

(4) The adsorption of IM+OP on the L245 steel surface is homogeneous and stable. It

does not readily suffer local damage. As a result, no pitting corrosion is observed

on L245 steel surface in stratum water with IM+OP in a H2S corrosion

environment at 75 C.

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24
Figure captions
Figure 1 Molecular structure of (a) octylphenol polyoxyethene ether (OP) and (b)

imidazoline quaternary ammonium salt (IM).

Figure 2 The synthetic route to the imidazoline quaternary ammonium salt (IM).

Figure 3 Open circuit potential and Tafel plots for L245 steel in the absence and

presence of various concentrations of imidazoline quaternary ammonium salt

(IM) and IM + octylphenol polyoxyethene ether (OP) inhibitors in H2S saturated

stratum water at 75C: (a) and (b) open circuit potentials; (c) and (d) Tafel plots.

Figure 4 The corrosion current density and the inhibition efficiency of L245 steel at

various concentrations of IM and IM+OP inhibitors derived from

potentiodynamic polarization curves in stratum water saturated with H2S at 75 C

(the scatter bands represent the standard deviations from 3 identical

measurements).

Figure 5 The (a) corrosion rate of L245 steel and the (b) inhibition efficiency by

weight loss after immersion in stratum water without inhibitor and after the

additions of 90 mg L-1 IM inhibitor and 90 mg L-1 IM+OP inhibitor for 168 h at

75 C (the scatter bands represent the standard deviations from 3 identical

measurements).

Figure 6 Surface morphologies of L245 steel after immersion in (a) stratum water

without inhibitor, (b) in stratum water with 90 mg L-1 IM inhibitor, (d) in

stratum water with 90 mg L-1 IM+OP inhibitor, (e) in stratum water with 180

mg L-1 IM inhibitor, (f) in stratum water with 180 mg L-1 IM+OP inhibitor, (g)

25
in stratum water with 360 mg L-1 IM inhibitor, (h) in stratum water with 360 mg

L-1 IM+OP inhibitor for 168 h at 75 C. In (c) the cross-section of the pit in (b)

is shown.

Figure 7 (a) Current and (b) potential curves recorded on L245 steel after immersion

in 3 wt% NaCl solution for 24 h; (c) Current and (d) potential curves recorded

on L245 steel after immersion in 3 wt% NaCl solution with 90 mg L-1 IM

inhibitor for 24 h; (e) Current and (f) potential curves recorded on L245 steel

after immersion in 3 wt% NaCl solution with 90 mg L-1 IM+OP inhibitor for 24

h.

Figure 8 Scanning electron microscope(SEM) analysis of L245 steel after immersion

(a) in 3 wt% NaCl solution, (b) in 3 wt% NaCl solution with 90 mg L-1 IM

inhibitor and (c) in 3 wt% NaCl solution with 90 mg L-1 IM+OP inhibitor for

30 s.

Figure 9 EDX-SEM microanalyses by element after immersion in (a) 3 wt% NaCl

solution with 90 mg L-1 IM inhibitor and (b) in 3 wt% NaCl solution with 90

mg L-1 IM+OP inhibitor for 30 s.

Figure 10 The surface morphologies of L245 steel obtained using scanning kelvin

probe force microscopy (SKPFM) after immersion for 30 s in (a) 3 wt% NaCl

solution without inhibitor, (b) 3 wt% NaCl solution with 90 mg L-1 IM inhibitor

and (c) 3 wt% NaCl solution with 90 mg L-1 IM+OP inhibitor; The surface

potentials of L245 steel obtained using SKPFM after immersion for 30 s in (d)

3 wt% NaCl solution without inhibitor, (e) 3 wt% NaCl solution with 90 mg L-1

26
IM inhibitor and (f) 3 wt% NaCl solution with 90 mg L-1 IM+OP inhibitor; (g)

shows the line analysis of surface potential in (d), (h) shows the line analysis of

surface potential in (e) and (i) shows the line analysis of surface potential in (f).

27
Figure
Fig. 1

(a)
CH3(CH2)7
O
(CH2CH2O)10

(b)
CH2CH2NH2
N
N Cl-

C17H33

28
Fig. 2
C17H33

CH3(CH2)7CH=CH(CH2)7COOH + H2N(CH2)2NH(CH2)2NH2 N N CH2CH2NH2

( Product I )
CH2Cl CH2CH2NH2
C17H33
N
N N CH2CH2NH2 N Cl-
+

C17H33

( Product II )

29
Fig. 3
-0.56 -1
-0.56

Open circuit potential (V vs. SCE)


-1
45 mg L IM
(b) 45 mg L IM+OP
Open circuit potential (V vs. SCE)

(a) 90 mg L IM
-1 -1
90 mg L IM+OP
-0.60 -0.60 -1
180 mg L IM
-1 180 mg L IM+OP
-1
360 mg L IM+OP
-1
360 mg L IM
-0.64 -0.64

-0.68 -0.68

-1
-0.72 0 mg L -0.72 -1
0 mg L

-0.76 -0.76
0 400 800 1200 1600 2000 0 400 800 1200 1600 2000
Time (s) Time (s)

-0.1 -1
-0.1 -1
0 mg L IM 0 mg L IM+OP
-0.2 (c) -1
45 mg L IM
-0.2 (d) -1
45 mg L IM+OP
-1
-1 90 mg L IM+OP
-0.3 90 mg L IM -0.3 -1
-1 180 mg L IM+OP
180 mg L IM
-0.4 -0.4 -1
E (V vs. SCE)

-1
360 mg L IM
E (V vs. SCE) 360 mg L IM+OP

-0.5 -0.5
-0.6 -0.6
-0.7 -0.7
-0.8 -0.8
-0.9 -0.9
-1.0 -1.0
-1.1 -6 -4 -3 -2 -1 -1.1 -6 -4 -3 -2 -1
-5 -5
10 10 10 10 10 10 10 10 10 10 10 10
-2 -2
log(I, A cm ) log(I, A cm )

30
Fig. 4

100 100
IM+OP
90 90

Inhibition efficiency (%)


Current density (A cm )

IM
-2

80 80
70 70
60 60
50 50
40 IM 40
30 30
20 IM+OP 20
10 10
0 0
0 30 60 90 120 150 180
Inhibitor concentration (mg L-1)

Fig. 5

31
(a) 0.45
0.40 -1
0 mg L
Corrosion Rate (mm y )
-1 0.35 -1
90 mg L
0.30 -1
180 mg L
0.25 -1
360 mg L
0.20

0.15
0.10
0.05
0.00

Uninhibited IM IM+OP

(b) 96
-1
90 mg L
Inhibition efficiency (%)

-1
92 180 mg L
-1
180 mg L
88

84

80
IM IM+OP

Fig.6

32
33
Fig.7

0.20 80 0.20 80

0.15
(a) 40
0.15
(b) 40

0
Potential (mV)
0

Potential (mV)
Current (A)
Current (A)

0.10 0.10
-40 -40
0.05 0.05
-80 -80
0.00 0.00
-120 -120
-0.05 -160 -0.05 -160

-0.10 -200 -0.10 -200


0 200 400 600 800 1000 0 200 400 600 800 1000
Time (s) Time (s)

0.20 80
(c) 40
0.15
0
Potential (mV)
Current (A)

0.10
-40
0.05
-80
0.00
-120
-0.05 -160

-0.10 -200
0 200 400 600 800 1000

Time(s)

34
Fig. 8

35
Fig. 9

Cl (IM)

Na (IM) N (IM) O (IM)

(a)

Cl (IM+OP)

Na (IM+OP) N (IM+OP) O (IM+OP)

(b)

36
Fig. 10

(a) (b) (c)

NaCl..Accumulation
of
(d) (e) (f)

2 (g) 2 (h) 2 (i) 0.3 m

1.9 m
1 1 1
Potential (V)
Potential (V)

Potential (V)

0 0 0

-1 -1 -1

-2 -2 -2

-3 -3 -3
0 2 4 6 8 10 12 14 16 0 2 4 6 8 10 0 2 4 6 8 10
Length (m ) Length (m ) Length (m )

37