Study On Initial Corrosion Behavior of Carbon Steel in Simulated Marine Industrial Atmosphere

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Study on initial corrosion behavior of

carbon steel in simulated marine
industrial atmosphere
2018-09-02
 Industry News
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Abstract:
Carbon steels as common structural material have been widely used for basic
facilities with the development of the city. In these service environments, carbon steel
would inevitably encounter the atmospheric corrosion. Especially, the corrosion of carbon
steels exposed to coastal-industrial atmosphere is very outstanding. However, the initial
corrosion mechanism of carbon steel subjected to coastal-industrial environment still need
to be clarified, which would be vital for predicating the subsequent corrosion process. In
addition, although many scholars studied the synergism of SO2 and Cl–, which obviously
accelerates the corrosion of steel and reduces its service life, there is few research about
the effect of the synergism of SO2 and Cl– (in different proportion) on the early corrosion
behavior of the carbon steel. Therefore, it is of great importance to investigate the initial
corrosion mechanism of carbon steel and the effect of the synergism of SO2 and Cl– (in
different proportion) in the coastal-industrial atmosphere. In present work, the initial
corrosion behavior of Q235 carbon steel exposed to a simulated coastal-industrial
atmosphere has been studied by weight loss, XRD, SEM and electrochemical
measurements. Also, the effect of the synergism of SO2 and Cl– (in different proportion)
on the early corrosion behavior of Q235 car bon steel has been investigated. The results
indicate that the initial corrosion behavior of carbon steel exposed to a simulated
coastal-industrial atmosphere presented a transition from corrosion acceleration to
deceleration, and the kinetics of accelerated corrosion process followed the empirical
equation D=Atn. A double-layered corrosion product was formed on the surface of carbon
steel after 24 h: the loose outer layer and relative dense inner layer; the synergistic effect
between SO2 and Cl– accelerated the corrosion of carbon steel. However, the change in
the ratio of SO2 and Cl– had no significant effect on the corrosion loss of carbon steel,
and had not changed the composition of corrosion products formed on carbon steel
surface. SO2 caused the corrosion morphology of carbon steel to tend to uniform
corrosion.
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Key words: carbon steel;atmospheric corrosion;synergism
GUO Mingxiao1,2, PAN Chen1, WANG Zhenyao1, HAN Wei1
 1 Institute of Metal Research, Chinese Academy of Sciences, Shenyang 110016,

China
 2 School of Materials Science and Engineering, University of Science and
Technology of China, Shenyang 110016, China
As the most commonly used structural material, carbon steel is widely used in
transportation, resource environment, energy power, construction and agriculture [1]. In
most cases, carbon steel is inevitably directly in contact with the atmosphere in the
service environment, and atmospheric corrosion occurs [2]. Therefore, research on
atmospheric corrosion of carbon steel has been receiving much attention. Wang Zhenduo
et al [3] conducted an experimental study on the corrosion of carbon steel under
atmospheric exposure, and summarized the climatic conditions and atmospheric
corrosivity of the natural environment in China. The results show that the climate of
different regions has different climate and the corrosion rate of carbon steel exists.
Significant differences. Some studies [4~7] have shown that the corrosion of carbon steel
exposed to the marine industrial atmosphere is particularly prominent. At present, many
southeast coastal cities in China are affected by the rapid development of industry, and
SO2 pollution is becoming more and more serious. It has developed into a marine
industrial atmosphere containing both Cl- and SO2. Therefore, it is necessary to carry out
research on the corrosion behavior of carbon steel in the marine industry atmosphere.
At present, research on the corrosion of steel in the atmosphere mainly focuses on
long-term corrosion behavior research. Kucera et al [8] conducted an 8 a exposure test in
Sweden and the Czech Republic. The results show that the corrosion rate of carbon steel
in a corrosive environment containing SO2 pollutants and chlorides can be described by a
linear equation, linear coefficient and SO2 deposition. Related. Liang Caifeng et al [9]
selected seven experimental points in China to carry out a 16-a exposure corrosion test
on 17 steels. The results show that the corrosion development of steel in the long-term
atmospheric environment follows the power function law. However, studies on the initial
corrosion behavior of carbon steel in the marine industry’s atmospheric environment have
rarely been reported. Since the corrosion products formed by carbon steel in the initial
stage of atmospheric corrosion exhibit different compositions and structures due to
differences in atmospheric environment, which significantly affect the subsequent
corrosion behavior of carbon steel, the corrosion behavior of carbon steel in the initial
stage is explored to understand the corrosion mechanism. It is important.
In addition, SO2 and Cl- are recognized as the most important corrosive components
affecting atmospheric corrosion in steel. Cai Jianping [10] studied the effects of chloride
and sulfur pollutants on atmospheric corrosion of carbon steel. The results show that there
is a synergistic effect in the initial stage of corrosion, but this synergistic effect is
weakened with the progress of corrosion. Qu Qing et al [11] explored the effect of NaCl
and low concentration of SO2 on the atmospheric corrosion behavior of A3 steel. The
results show that due to the synergy between NaCl and low concentration of SO2, the
corrosion loss of steel is much greater than that caused by 2 alone. The corrosion is
weightless. It can be seen that in the atmospheric environment of marine industry, the
synergistic effect of SO2 and Cl- can significantly accelerate the corrosion damage of
steel and reduce its service life [12~14]. However, the mechanism of the effect of the ratio
of SO2 to Cl- on the synergistic effect of carbon steel initial corrosion behavior is still
unclear and needs further detailed study.
In summary, this work carried out the laboratory simulation acceleration method, using
traditional weightless analysis, scanning electron microscopy, X-ray diffraction (XRD)
analysis and electrochemical testing methods to carry out the initial corrosion behavior
mechanism of carbon steel in the simulated marine industrial atmosphere. Detailed study
and further study the effects of different ratios of SO2 and Cl- on the initial corrosion
behavior of carbon steel.
1 Experimental method
1.1 Experimental materials
The experimental material is Q235 steel, and its chemical composition (mass fraction, %)
is: C 0.18, Si 0.25, Mn 0.5, S 0.018, P 0.016, Fe balance. The sample size for weight loss
analysis and rust layer analysis is 50 mm × 25 mm × 2.5 mm. All the samples were
degreased by acetone mechanical cleaning before the experiment, then dehydrated with
alcohol and placed in a desiccator for use. After 24 h, the weight loss analysis samples
were weighed and recorded with an analytical balance with an accuracy of 0.001 g. The
sample size for electrochemical analysis was 10 mm × 10 mm × 2.5 mm.
1.2 Laboratory accelerated simulation experiment
Accelerated corrosion experiments were carried out using a C4-180Pro high and low
temperature damp heat test chamber. Because HSO3- is more in line with the conversion
behavior and characteristics of SO2 under the liquid film in the corrosion process, this
experiment uses NaHSO3 and NaCl to simulate SO2 and Cl- in the atmosphere, and
builds a laboratory simulation accelerated experimental method. The NaHSO3 and NaCl
solutions were used as the corrosive medium. The corrosive medium was evenly spread
on the surface of the sample by a micro-syringe, then placed in an oven for drying, and
finally placed in a test chamber for accelerated corrosion experiments. The experiment
was carried out according to the “wet/dry” alternating method, and it was cycled every 3 h,
in which it was wet (relative humidity 90%, temperature 30 °C) for 1 h, dry (relative
humidity 60%, temperature 30 °C) for 2 h, every 24 h. Deposit the salt once. In order to
deepen the understanding of the synergistic effect of SO2 and Cl-, and at the same time, it
is beneficial to realize the control of the corrosion behavior of carbon steel under different
corrosive environments. This work also utilizes the indoor dry-wet alternate cycle
accelerated corrosion test method, the amount of S and Cl substances. Under the
premise of constant, the effects of different ratios of SO2 and Cl- on the initial corrosion
behavior of carbon steel were investigated by adjusting the ratio of NaHSO3 and NaCl in
the corrosive medium, and the synergistic mechanism of SO2 and Cl- was further
revealed. The following two sets of accelerated corrosion experiments were carried out
according to the above-mentioned dry-wet alternating experimental method:
(1) Accelerate experiment 1 to simulate the initial corrosion behavior of carbon steel in the
atmospheric environment of marine industry. 0.15 mol/L NaCl+0.05 mol/L NaHSO3 (the
amount of salt deposited on the surface of the sample was 10 μL/cm2, and the mixed salt
ratio was 3:1) was deposited as a corrosive medium on the surface of the sample for
accelerated dry-wet cycle alternating corrosion accelerated experiment. . The
experimental periods were 24, 48, 72, 96 and 120 h, respectively. Three parallel samples
were taken for each weight loss analysis, one for morphology analysis, and four
electrochemical parallel samples.
(2) Accelerated experiment 2, the effect of different ratios of SO2 and Cl- synergy on the
initial corrosion mechanism of carbon steel. Single NaCl (0.2 mol/L NaCl), single NaHSO3
(0.2 mol/L NaHSO3) and different ratios of NaCl and NaHSO3 mixed salt (0.15 mol/L
NaCl+0.05 mol/L NaHSO3, 0.1 mol/L NaCl+0.1 mol) /L NaHSO3, 0.05 mol/L NaCl+0.15
mol/L NaHSO3), ie, the mixing ratio is 3:1, 1:1, 1:3, respectively, deposited as corrosion
medium on the surface of the sample for alternating wet and dry cycle corrosion test The
experimental period is 120 h.
1.3 Analysis of corrosion weight loss
The sample was derusted using 500 mL HCl (38% concentrated hydrochloric acid) + 500
mL distilled water + 20 g hexamethylenetetramine solution. After the rust removal, the
sample was washed with distilled water and alcohol, finally blown dry with a hair dryer,
placed in a desiccator, and weighed after 24 h (accurate to 0.001 g). The weight loss data
for each cycle takes the average of the weight loss data of three parallel samples.
1.4 analysis of rust layer composition
A 50 mm × 25 mm × 2.5 mm sample taken for each rust layer analysis in each cycle was
cut into small pieces of 10 mm × 10 mm × 2.5 mm with a saw, and then the composition of
the rust layer was analyzed. The Rigaku-D/max-2500PC XRD was used for phase
analysis. The Cu target was used to qualitatively analyze the corrosion products at a
scanning rate of 2 °/min at 50 kV and 250 mA.
1.5 rust layer morphology analysis
The surface morphology and cross-section of the corrosion samples were observed and
analyzed by ESEM XL30 FEG scanning electron microscopy (SEM). The rust layer
cross-section analysis sample was encapsulated with epoxy resin at room temperature.
After curing, it was sanded from No. 600 to No. 2000 with sandpaper, then polished with
W2.5 abrasive paste. After polishing, it was washed with alcohol and blown under a hair
dryer. dry. Finally, the sample was placed under SEM for observation.
1.6 Electrochemical analysis
Electrochemical measurements were performed using a PARSTAT 2273 electrochemical
workstation using a standard three-electrode system with a saturated calomel electrode
(SCE) as the reference electrode, a Pt electrode as the auxiliary electrode, and a
corrosion sample as the working electrode. The potentials measured in the experimental
results are all potentials relative to SCE. The electrolyte was a 0.1 mol/L Na2SO4 solution
prepared from analytically pure reagent and distilled water, and the experimental
temperature was room temperature. The scanning rate of the potentiodynamic
polarization curve was 0.33 mV/s. Since the self-corrosion potential of the working
electrode is unstable at the beginning of the measurement, it is necessary to stabilize until
the open circuit potential does not exceed 1 mV within 1 min before performing the above
electrochemical test.
2 Experimental results and analysis
2.1 Initial corrosion mechanism of Q235 carbon steel in simulated atmospheric
environment of marine industry
2.1.1 Corrosion Dynamics The weight loss measurement method is the most commonly
used method for atmospheric corrosion evaluation and is usually expressed by the weight
loss per unit surface area or the average corrosion depth. The corrosion depth of steel can
be obtained by the following formula [15]:
Where D is the corrosion depth, μm; Wt is the corrosion weight loss, g; ρ is the density of
Q235 carbon steel, 7.86 g/cm3; S is the total area of the sample, cm2.
According to the corrosion depth of carbon steel, the average corrosion rate Va can be
calculated by the following formula [15]:
Where t is the corrosion time, h; the subscript m represents the sampling period (when m
= 1, it represents corrosion for 24 h, and so on, when m = 2, 3, 4, 5, the corrosion time is
48, 72, 96, 120 h). Figure 1 shows the trend of the average corrosion rate of carbon steel
in the atmospheric environment of simulated marine industry with corrosion time. It can be
seen that the average corrosion rate of carbon steel increases gradually throughout the
corrosion cycle, reaching a maximum at 96 h of corrosion, and then the corrosion rate
drops significantly. That is to say, the initial corrosion process of Q235 carbon steel in this
environment is divided into two stages, namely the corrosion acceleration process and the
corrosion deceleration process. This phenomenon should be closely related to the
evolution process of carbon steel surface corrosion products.
Fig.1 Average corrosion rates of Q235 carbon steel exposed to a simulated

coastal-industrial atmosphere as a function of exposure time
The traditional view is that the law of long-term atmospheric corrosion dynamics of steel
follows the law of power function, as shown in the following equation [15]:
Where A and n are constants whose values are related to the material and the corrosive
environment. In order to verify whether the power function law is applicable to the
development of corrosion kinetics of carbon steel in the atmospheric environment of the
marine industry, especially the dynamic development law of the initial corrosion
acceleration process, the power function relationship is used to simulate the marine
industry of Q235 carbon steel. The weight loss data of the initial corrosion acceleration
stage (first 96 h) in the atmospheric environment was fitted, and the fitting results are
shown in Fig. 2. The correlation coefficient R2 (0.9998) is close to 1, indicating that the
initial corrosion behavior of carbon steel in the simulated marine industrial atmosphere still
follows the law of power function development. In this experiment, n=1.3998, which is
greater than 1, indicating that the rust layer formed by carbon steel in the initial stage of
corrosion has no protection to the substrate. With the extension of the corrosion cycle (the
first 96 h), the corrosion rate of carbon steel increases gradually.
Fig.2 Thickness reductions of Q235 carbon steel exposed to a simulated

coastal-industrial atmosphere as a function of exposure time
2.1.2 Composition of rust layer Figure 3 shows the XRD spectrum of corrosion products
formed on the surface of Q235 carbon steel in different atmospheric corrosion
environments under simulated atmospheric conditions. It can be seen that the corrosion
products mainly have α-FeOOH and γ-FeOOH after 24 h of corrosion, and a small amount
of FeSO32.5H2O is also detected. For the initial stage of carbon steel corrosion, the
corrosion products are mainly γ-FeOOH, and the presence of SO2 promotes the
preferential generation of α-FeOOH [16]. When corroded to 48 h, β-FeOOH began to
appear in the corrosion products, and the formation of β-FeOOH was related to the
presence and concentration of Cl-. At this time, the Cl- concentration on the surface of the
sample reaches a critical concentration, which provides the necessary conditions for the
formation of β-FeOOH. β-FeOOH has a strong reducing activity, which promotes the
corrosion process [17]. After that, as the corrosion time prolonged, the composition and
relative content of the corrosion products no longer changed significantly. In addition, the
presence of the corrosion product FeSO32.5H2O can always be detected throughout the
corrosion process. The ferrous sulfate salt increases the conductivity of the thin liquid film
and promotes the electrochemical corrosion reaction on the surface of the sample. At the
same time, according to the acid regeneration cycle mechanism, FeSO3 will be formed
into oxygen by FeSO4, and then FeSO4 is hydrolyzed and oxidized to form iron
oxyhydroxide. And free sulfuric acid [18,19], thereby accelerating atmospheric corrosion
of carbon steel.
Fig.3 XRD patterns for the scraped rust formed on Q235 carbon steel surface after
different exposure time
2.1.3 Analysis of rust layer morphology Macroscopically, as the exposure time is

prolonged, the color of the corrosion product gradually deepens, and the orange-yellow
color changes to reddish brown and tan, and the corrosion products are evenly distributed
on the surface of the sample. Figure 4 is a diagram showing the surface topography of
rust layer in different corrosion cycles of Q235 carbon steel in simulated marine industrial
atmosphere. At the first 24 h of corrosion, spherical corrosion products formed and the
corrosion product layer was very thin, which caused the corrosive medium to easily
contact the substrate and cause corrosion [20] (Fig. 4a). When the corrosion time was
extended to 48 h, the surface of the sample was corroded. The product gradually
increases, but the corrosion product contains a large number of pores, which can not
effectively prevent the intrusion of corrosive media (Fig. 4b); and then, as the corrosion
time prolongs, the surface corrosion product compactness gradually increases (Fig.
4c~e).
Fig.4 Surface morphologies of Q235 carbon steel exposed to a simulated coastal-

industrial atmosphere for 24 h (a), 48 h (b), 72 h (c), 96 h (d) and 120 h (e)
Figure 5 is a cross-sectional view of the cross-section of the rust layer of Q235 carbon
steel under different atmospheric corrosion conditions in a simulated marine industrial
atmosphere. At the first 24 h of corrosion, the rust layer is thinner and looser. There are
many transverse and longitudinal cracks, which have no inhibitory effect on O2 and
aggressive media, and the corrosion products have little protection to the steel matrix.
When corroded to 72 h, the corrosion products showed obvious delamination, that is, the
loose rust layer with a large number of holes and the cracked but relatively dense inner
rust layer [21, 22], but the inner rust layer and the outer rust layer The boundaries
between the two are not obvious. With the prolongation of corrosion time, the thickness of
the inner and outer rust layers gradually increases and the compactness gradually
increases. When corroded to 120 h, the inner layer corrosion products are dense and
crack-free, which can effectively prevent the penetration of O2 and corrosive media. The
corrosion rate of steel begins to decrease.
Fig.5 Cross-sectional morphologies of Q235 carbon steel exposed to a simulated

coastal-industrial atmosphere for 24 h (a), 48 h (b), 72 h (c),96 h (d) and 120 h (e)
2.1.4 Electrochemical analysis Figures 6 and 7 show the potentiodynamic polarization

curves of the rust and blank samples of carbon steel in different corrosion cycles in 0.1
mol/L Na2SO4 solution and the corrosion current density obtained by fitting. It can be
seen from the figure that the cathode process of the blank sample is controlled by the
diffusion diffusion of dissolved oxygen, and the cathode current density of the rust sample
is significantly larger than that of the blank sample, which is mainly related to the reduction
of the cathode corrosion product of the rust sample. After 24~72 h corrosion, the cathode
current density of the rust sample increased gradually, indicating that the reduction
reaction of the corrosion product gradually became the main cathode process. After 96 h
of corrosion, the cathode current density did not change much, indicating that the cathodic
reduction process gradually became stable. Stabilization of the cathode process with rust
samples may be related to the stabilization of the relative content of γ-FeOOH in the
corrosion products [23].
For the anode process, the anode reaction of the rust sample is in addition to the
dissolution reaction of the carbon steel matrix, and the oxidation reaction of the corrosion
product FeSO3 is performed, and the anode current density of the rust sample is larger
than that of the blank sample. However, it is worth noting that as the corrosion time
prolongs, the anode current density of the rust sample decreases gradually, indicating that
the anode reaction process is gradually suppressed. The corrosion current density
obtained by curve fitting is shown in Fig. 7. Corrosion current density of rust samples
increased significantly after 24~72 h of corrosion. After 72 h of corrosion, the corrosion
current density of rust samples increased, and the change became stable. This result is
consistent with the corrosion rate results obtained from the weight loss curve.
Fig.6 Potentiodynamic polarization curves of Q235 carbon steel with different exposure
time (E—potential, i—current density)
2.1.5 Analysis of initial corrosion evolution process In the simulated atmospheric

environment of marine industry, Q235 carbon steel undergoes corrosion process of matrix
anode dissolution and dissolved oxygen cathode reduction under a thin liquid film, thereby
forming a hydrolyzate layer of Fe(OH)2, followed by During the drying process, Fe(OH)2
is oxidized by air to form a large amount of divalent and trivalent oxides and hydroxides of
Fe, and some oxides are converted into γ-FeOOH and α-FeOOH. The presence of SO2
promotes α-FeOOH. Priority generation. When corroded to 48 h, the concentration of Cl-
reached a critical concentration, which provided the necessary conditions for the
formation of β-FeOOH. At this time, β-FeOOH began to appear in the corrosion products.
HSO3- in the simulated environment makes the thin liquid film on the sample surface
acidic, resulting in a uniform chemical dissolution reaction [24], and FeSO32.5H2O is
gradually formed on the surface of Q235 carbon steel. In the initial stage of corrosion, the
rust layer is thin, and the outer rust layer is loose, and the inner rust layer is cracked (Fig.
5). Such corrosion products can not effectively block the corrosion of the corrosive
medium, but can prolong the time that the corrosive medium stays on the surface of the
carbon steel. That is, prolonging the surface wetting time and promoting the rapid
development of corrosion, the corrosion rate is gradually increased. Until corrosion for 120
h, the thickness of the inner and outer rust layers increases, the compactness increases,
and the cracks decrease. The corrosion products can effectively block the intrusion of O2
and corrosive media, providing some protection for the matrix, which shows that the
corrosion rate begins to decrease.
Fig.7 Corrosion current densities (icorr) of corroded Q235 carbon steel as a function of
exposure time
2.2 Effect of different ratios of SO2 and Cl- on initial corrosion mechanism
2.2.1 Analysis of corrosion weight loss Figure 8 shows the corrosion depth of Q235
carbon steel after corrosion for 120 h in different corrosive media. It can be seen that the
corrosion weight loss of carbon steel in SO2 and Cl-mixed corrosive medium environment
is significantly greater than that of single corrosive medium, indicating that there is a
synergistic effect between SO2 and Cl- in the corrosion process, which accelerates the
corrosion of carbon steel [25~28]. The corrosion effect of corrosive medium on Q235
carbon steel is: NaHSO3+NaCl>NaHSO3>NaCl. Among them, when the ratio of
NaCl:NaHSO3 is 1:1, the corrosion loss of carbon steel reaches a maximum value.
Fig.8 Thickness losses of Q235 carbon steel exposed to different corrosive mediums for
120 h
Cl- is a natural pollutant that is found in the ocean atmosphere. Due to its small volume,
Cl- can pass through the rust layer to reach the surface of the substrate to promote the
corrosion reaction, and is not consumed during the reaction, acting as a catalyst [29, 30].
At the same time, the presence of Cl- increases the conductivity of the thin liquid film and
promotes the role of corrosion of the microbattery. The presence of Cl- also causes partial
dissolution of Fe(OH)2 adsorbed by the Fe matrix:
The above effects may cause localized dissolution of the relatively dense corrosion
products to cause loose outer rust layers and fine cracks (Fig. 5). O2 and corrosive media
are transmitted to the surface of the substrate through cracks to promote corrosion.
SO2 is recognized as the most corrosive gas in the atmosphere. In this experiment,
HSO3- reacts with the matrix to form FeSO3, while FeSO3 is gradually oxidized to FeSO4,
and then FeSO4 is hydrolyzed and oxidized to form oxyhydroxide and free sulfuric acid:
H2SO4 accelerates the corrosion of Fe:
The newly formed FeSO4 is hydrolyzed to the free acid, so that it can reciprocate, so that
one molecule of SO2 can generate many molecules of rust [31~33], and the free acid
generated during the cycle dissolves the unstable corrosion products in the rust layer.
Provides a channel for the intrusion of O2 and corrosive media to further accelerate
corrosion. The synergistic effect of the local dissolution of the corrosion products and the
regeneration cycle of the acid makes the corrosion weight loss of the Q235 carbon steel in
the mixed corrosive medium significantly higher than that in the single corrosive medium.
However, this synergistic effect does not continue to increase with increasing SO2
concentration in the corrosive medium, but the corrosion weight loss of carbon steel
reaches a maximum when the ratio of Cl- and SO2 is 1:1. This is because as the
concentration of SO2 increases, the amount of H2SO4 generated during the regeneration
cycle of the acid increases, and the rust layer is more easily destroyed, so that the
corrosion accelerates. However, when the SO2 concentration continues to rise to a
certain critical value, SO2 significantly promotes the formation of the corrosion product
α-FeOOH. α-FeOOH is a stable corrosion product with good continuity and compactness,
which can provide good protection to the substrate, which shows that the corrosion weight
loss of carbon steel decreases. However, the effect of the ratio of SO2 and Cl- in the
corrosive medium on the corrosion weight loss of carbon steel is not significant, indicating
that the effect of the ratio of SO2 and Cl- on the synergy is not obvious.
2.2.2 Corrosion product composition analysis Figure 9 shows the XRD spectrum of Q235
carbon steel after corrosion for 120 h in a single NaCl, NaHSO3 corrosive medium and
different ratios of NaCl and NaHSO3 corrosion media. It can be seen that the corrosion
products formed in different proportions of mixed medium mainly include α-FeOOH,
β-FeOOH, γ-FeOOH and FeSO32.5H2O, indicating that the ratio of SO2 to Cl- in the
corrosive medium does not change the corrosion products formed on the surface of
carbon steel. Ingredients, but as the proportion of NaCl decreases, the relative content of
β-FeOOH in the corrosion products decreases significantly, while the relative content of
α-FeOOH gradually increases. The simultaneous presence of β-FeOOH and
FeSO32.5H2O promotes the corrosion process, which shows that the corrosion weight
loss of carbon steel in mixed corrosive media is significantly higher than that of single
corrosive media. Q235 carbon steel in a single NaCl corrosion environment, the corrosion
products contain a large amount of β-FeOOH and a small amount of γ-FeOOH, because
the presence of high concentration of Cl- promotes the formation of β-FeOOH; and in the
case of corrosion in a single NaHSO3 environment, The corrosion product contains a
large amount of α-FeOOH and a small amount of γ-FeOOH, and it can be seen that
α-FeOOH is preferentially formed in an environment containing SO2 [16].
Fig.9 XRD patterns for the scraped rust formed on Q235 carbon steel exposed to different
corrosive mediums for 120 h(a) the mixed corrosive mediums(b) the single corrosive
mediums
2.2.3 Analysis of Corrosion Product Morphology Figure 10 shows the cross-sectional

shape of carbon steel after corrosion for 120 h in different corrosive media. It can be seen
from the figure that when Q235 carbon steel is corroded in the environment of single NaCl,
the rust layer is thin, but there is a large local corrosion pit, which is caused by NaCl
induced pitting; when Q235 carbon steel exists in single NaHSO3 When corroded in the
environment, the rust layer is also very thin, but there is no significant local corrosion
compared to the single NaCl environment.
Fig.10 Cross-sectional morphologies of Q235 carbon steel exposed to different corrosive

mediums for 120 h
(a) NaCl (b) NaCl∶NaHSO3=3∶1 (c) NaCl∶NaHSO3=1∶1 (d) NaCl∶
NaHSO3=1∶3 (e) NaHSO3
When Q235 carbon steel is corroded in the environment where both NaCl and NaHSO3
coexist, the thickness of corrosion products formed is significantly higher than that of
single corrosive medium, indicating that the corrosion rate of Q235 carbon steel in NaCl
and NaHSO3 mixed corrosion medium is faster, the result and weightlessness. The
results are consistent. It is worth noting that the corrosion product layer of Q235 carbon
steel in a 3:1 ratio of NaCl and NaHSO3 corrosive medium is a two-layer structure, that is,
a loose, porous outer layer structure and a relatively dense inner layer structure [ 21, 22],
and this corrosion product stratification is not clearly observed in other mixed proportions
of the corrosive environment. Due to the presence of Cl-, the corrosion products formed
on the surface of the carbon steel are locally dissolved. The higher the Cl- concentration,
the more severe the local dissolution of the corrosion products, resulting in a loose outer
layer structure of the corrosion products, thereby inferring the surface of the carbon steel.
The stratification of corrosion products is related to the Cl- concentration in the corrosive
medium.
Figure 11 shows the surface topography of Q235 carbon steel after corrosion for 120 h in
different corrosive media. It can be seen from the figure that when the carbon steel is
corroded in a single NaCl, the surface of the sample after removing the corrosion product
exhibits atypical local corrosion characteristics, and the corrosion pit is large and small,
which is caused by NaCl (Fig. 11a); When carbon steel is corroded in the mixed medium
of NaCl and NaHSO3, it can be seen that the corrosion pit on the surface of the sample is
small and much, and the corrosion pit of the surface becomes more as the proportion of
NaHSO3 in the mixed corrosion medium increases. Small and dense (Fig. 11b~d); when
carbon steel is corroded in a single NaHSO3, the surface of the sample exhibits its own
uniform corrosion characteristics (Fig. 11e). The above analysis shows that when carbon
steel is corroded in the environment where SO2 and Cl- coexist, SO2 promotes the
corrosion pattern of carbon steel to tend to uniform corrosion.
Fig.11 Morphologies of Q235 carbon steel exposed to different corrosive mediums after
removing corrosion products for 120 h(a) NaCl (b) NaCl∶NaHSO3=3∶1 (c) NaCl∶
NaHSO3=1∶1 (d) NaCl∶NaHSO3=1∶3 (e) NaHSO3
2.2.4 Electrochemical analysis Figure 12 shows the potentiodynamic polarization curves

of Q235 carbon steel after corrosion for 120 h in different corrosive media. It can be seen
from the figure that the cathode current density of Q235 carbon steel when corroded in a
single NaHSO3 is significantly smaller than the cathode current density corroded in a
single NaCl. The reason for the analysis is that the corrosion product is mainly β-FeOOH
when corroded in a single NaCl, and the α-FeOOH is mainly corroded in NaHSO3. The
reduction of α-FeOOH is less than that of β-FeOOH, so the corrosion of the corrosion
product β-FeOOH is more active when corroded in a single NaCl, which is characterized
by a higher cathode current density. Although the carbon steel is corroded in a single
NaHSO3, the cathode process is somewhat inhibited, but the anode process is
significantly promoted. This is because the corrosion product of carbon steel in a single
NaHSO3 environment contains FeSO3, that is, the anode reaction process In addition to
the carbon steel matrix dissolution reaction, there is also the oxidation reaction of the
corrosion product FeSO3, so the anode current density is significantly higher than the
anode current density of the carbon steel corroded in a single NaCl. Corrosion current
density of rust samples after corrosion of Q235 carbon steel in different corrosive media
for 120 h was obtained according to the results of dynamic potential polarization curves
(Fig. 13). It can be seen that the corrosion current density of Q235 carbon steel in different
NaCl and NaHSO3 mixed medium environments is comparable, but significantly greater
than its corrosion current density in single NaCl and single NaHSO3; the corrosion current
density of carbon steel in a single NaHSO3 environment is greater than that in single
Corrosion current density in NaCl. This result is consistent with the corrosion weight loss
results.
Fig.12 Potentiodynamic polarization curves of Q235 carbon steel exposed to different

corrosive mediums for 120 h
Fig.13 icorr of Q235 carbon steel exposed to different corrosive mediums for 120 h
3 Conclusion
(1) The initial corrosion rate of Q235 carbon steel in the simulated marine industrial
atmosphere first increased and then decreased. The dynamics of corrosion acceleration
process still followed the power function formula D=Atn.
(2) The presence of corrosion products β-FeOOH and FeSO3 promotes an increase in the
corrosion rate of carbon steel. After 24 h of corrosion, the corrosion product has a loose
outer layer and a relatively dense inner layer structure. The leaching of corrosion products
may be related to the Cl- concentration in the corrosive medium.
(3) At the initial stage of corrosion, the synergistic effect of SO2 and Cl- accelerates the
corrosion of carbon steel, but the change of the ratio of SO2 and Cl- in the corrosive
medium has no obvious effect on the corrosion weight loss and does not change the
corrosion product composition formed on the surface of carbon steel. SO2 promotes the
corrosion pattern of carbon steel to tend to uniform corrosion.
The authors have declared that no competing interests exist.
Source: China Pipe Fittings Manufacturer – Yaang Pipe Industry

(www.metallicsteel.com)
(Yaang Pipe Industry is a leading manufacturer and supplier of nickel alloy and stainless
steel products, including Super Duplex Stainless Steel Flanges, Stainless Steel Flanges,
Stainless Steel Pipe Fittings, Stainless Steel Pipe. Yaang products are widely used in
Shipbuilding, Nuclear power, Marine engineering, Petroleum, Chemical, Mining, Sewage
treatment, Natural gas and Pressure vessels and other industries.)
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Atmosphere. Acta Metall, 2018, 54(1): 65-75.

Study On Initial Corrosion Behavior of Carbon Steel in Simulated Marine Industrial Atmosphere

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Study on initial corrosion behavior of

Key words: carbon steel;atmospheric corrosion;synergism

GUO Mingxiao1,2, PAN Chen1, WANG Zhenyao1, HAN Wei1

 1 Institute of Metal Research, Chinese Academy of Sciences, Shenyang 110016,

Fig.1 Average corrosion rates of Q235 carbon steel exposed to a simulated

first 96 h), the corrosion rate of carbon steel increases gradually.

Fig.2 Thickness reductions of Q235 carbon steel exposed to a simulated

2.1.3 Analysis of rust layer morphology Macroscopically, as the exposure time is

Fig.4 Surface morphologies of Q235 carbon steel exposed to a simulated coastal-

Fig.5 Cross-sectional morphologies of Q235 carbon steel exposed to a simulated

2.1.4 Electrochemical analysis Figures 6 and 7 show the potentiodynamic polarization

2.1.5 Analysis of initial corrosion evolution process In the simulated atmospheric

H2SO4 accelerates the corrosion of Fe:

α-FeOOH is preferentially formed in an environment containing SO2 [16].

2.2.3 Analysis of Corrosion Product Morphology Figure 10 shows the cross-sectional

Fig.10 Cross-sectional morphologies of Q235 carbon steel exposed to different corrosive

2.2.4 Electrochemical analysis Figure 12 shows the potentiodynamic polarization curves

Fig.12 Potentiodynamic polarization curves of Q235 carbon steel exposed to different

Source: China Pipe Fittings Manufacturer – Yaang Pipe Industry

• Failure Analysis on Natural Gas Pipeline of 20 Steel and 16Mn Steel

Czechoslovakia [J]. Key Eng. Mater., 1988, 20-28: 167

hull steel[J]. Equip. Environ. Eng., 2012, 9(3): 66

Corrosion Behavior of Carbon Steel Exposed to a Simulated Coastal-Industrial

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