1096 Liu, Xu, Zhu and Meng Materials and Corrosion 2014, 65, No.

11

Pitting corrosion of 13Cr steel in aerated brine completion

fluids
Y. Liu, L. N. Xu*, J. Y. Zhu and Y. Meng

Corrosion behavior of 13Cr steel in aerated Br
containing brine completion

fluids at 150 8C was studied. A series of corrosion tests with different test
duration of 7, 15, 30, and 60 days were performed in an autoclave to investigate
the corrosion rate, morphology, and pitting evolution. Cross‐sectional
morphologies of the corrosion products were observed by scanning electron
microscopy (SEM). Energy dispersive spectrum (EDS) was used to study the
element distribution of the corrosion product inside the pits. The results showed
that 13Cr steel emerged out of slight pitting corrosion, with the pitting growth
rate of 0.04 mm/year. The pitting corrosion occurred after corroded 15 days, and
the pits were filled with bromide salt. It is deduced that Br was involved in both
the breakdown of the passive film and the expansion of the pits.

1 Introduction adsorption on the film surface. The aggressiveness of X on

The corrosion of casing and tubing in the brine completion fluids
has been a research hotspot in the course of oil and gas
exploitation [1–3]. The brine completion fluids are applied to deep
wells (the average depth >6000 m) and the temperature is very
high about 150 8C [4,5]. In order to balance the high formation
pressure of deep well and maintain the borehole stability,
brine completion fluids with high density are needed at high
temperature [6,7]. The brine completion fluids usually consist of
halide salts (such as NaCl, KCl, ZnCl2, and bromide), which are
corrosive to 13Cr steel [8–10]. Due to better corrosion resistance
and lower cost in comparison with other stainless steels such as
duplex stainless steel, 13Cr steel as the casing is widely used in oil
and gas field [11].
Many scholars have investigated the pitting corrosion of 13Cr
steel in traditional Cl
containing brine environment for several
years [12,13]. Pfennig et al. [14] found that severe pitting corrosion
with pit depths around 1.4 mm appeared on the X46Cr13 steel
after 200 h of exposure in CO2‐saturated brine at 60 8C and
0.1 MPa in Cl
containing saline aquifer water. Yin et al. [15]
revealed that lots of pits were formed at the localized corrosion
areas of metal surface in simulated oilfield solution at high
temperature, which confirmed that high concentration of Cl
did
initiate pitting. Refaey et al. [16] pointed out that the pitting
corrosion resistance of the passive film decreased with the
increasing of X (Cl
or Br
) concentration to competitive
Y. Liu, L. N. Xu, J. Y. Zhu, Y. Meng
Key Laboratory for Environmental Fracture (MOE), Institute of
Advanced Materials and Technology, University of Science and
Technology Beijing, Beijing 100083, (P. R. China)
E-mail: xulining@ustb.edu.cn
corrosion of stainless steel decreased in the order of Cl
> Br
.
However, the pitting corrosion resistance performance of
13Cr steel in Br
containing brine completion fluids is rarely
studied. Therefore the aim of this paper is to highlight the effect
and the mechanism of bromine ions on the corrosion of 13Cr
steel in aerated brine completion fluids environment at high
temperature (150 8C), which provides a reference to the selection
of brine completion fluids in the deep wells environment.
2 Experimental
The chemical composition of the 13Cr steel is shown in Table 1. The
specimens for tests were machined with dimensions of 50  10 
3 mm3. All the specimens were subsequently polished with 360,
800 grit silicon carbide paper, rinsed with deionized water, and
degreased in acetone. Before each test, the specimens were weighed
with an analytical balance with an accuracy of 10
4 g.
The test solution was made from deionized water and salts to
simulate brine completion fluids. The major composition is
8.0  10
1 mol/L K3PO4, 6.0  10
3 mol/L KBr, 1.0  10
3 mol/L
CaBr2, and 4.0  10
4 mol/L KOH.
Corrosion tests were conducted in a 3 L autoclave to
investigate corrosion rate and corrosion morphology. The total
pressure was 3 MPa, which was achieved by purging synthetic air
(21% O2 þ 79% N2) at 150 8C. The duration of the tests was 7, 15,
30, and 60 days, respectively. After each test, the corrosion
product film was removed, and then the weight of the specimen
was measured. The corrosion rates measured by weight loss were
reported in accordance with ASTM G31. Energy dispersive X‐ray
spectroscopy (EDS, Kevex SuperDry) and scanning electron
microscopy (SEM, LEO‐1450) analysis were employed to analyze
the composition and morphology of the corrosion products.

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Materials and Corrosion 2014, 65, No. 11
Table 1. Chemical composition (wt%) of 13Cr stainless steel
C Cr Mn Si P S V Fe
0.027 12 0.22 0.30 0.014 0.0035 0.041
3 Results
According to ASTM G31, the average corrosion rate rc was
calculated on the basis of Equation (1):
8:76  104 ðm
m t Þ
rc ¼
Str
where rc is average corrosion rate, mm/year; m is the mass of the
specimen before the test, g; mt is the mass of the specimen after
the removal of corrosion product, g; S is the exposed surface area
of the specimen, cm2; r is the density of the specimen, g/cm3; and
t is the test duration, h.
The weight loss and average corrosion rate of 13Cr in brine
completion fluids solution containing bromine ions at 150 8C
under different test durations is shown in Table 2.
The results demonstrated that 13Cr stainless steel endured
low average corrosion rate at 150 8C, in presence of O2, Br
in the
solution. The average corrosion rate was only 0.0135 mm/year at
the exposure of 60 days. The pH value of the test solution was
about 10.89. Since the solution was alkaline, and filled with
oxygen, the stainless steels are susceptible to being in a passive
Figure 1. Macroscopic morphologies of 13Cr stainless steel samples after different test durations after corrosion test: (a) before test; (b) 7 days;
(c) 15 days; (d) 30 days; (e) 60 days
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Pitting corrosion of 13Cr steel 1097
Table 2. Weight loss and average corrosion rate of 13Cr stainless steel
after different test durations
Time (days) 7 15 30 60
Bal.
m
mt (g) 0.0128 0.0158 0.0137 0.0231
rc (mm/year) 0.0661 0.0371 0.0161 0.0135
state [17,18]. The average corrosion rate dropped gradually with
the increase of the test duration, which indicated the corrosion
product film became more protective with the increasing of time.
Figure 1a shows the original surface of 13Cr sample.
ð1Þ
Figure 1b–e shows the macroscopic morphologies of 13Cr
specimens after different test durations after corrosion test. As
shown in Fig. 1b, it seems that a very thin corrosion product film
was present on the surface of the specimen after the corrosion
time of 7 days. After that, the sample surface had lost its own
metallic luster, as shown in Fig. 1c–e. For 60 days, salt particles
precipitated from the test solution and covered the sample
surface, forming a tight, complete light green film, as shown in
Fig. 1e. With the increases of test duration, particles on the sample
surface grew up gradually, so did the thickness of salt films.
The SEM images of specimens after different test duration
were presented in Fig. 2. As shown in Fig. 2a, there was a thin film
on the specimen surface after corroded 7 days. The EDS analysis
result showed that the main composition of the film consisted of
Fe, Cr, and O (Table 3), which indicated it was a passive film. The
composition of the particle was analyzed by EDS, and the result
© 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
1098 Liu, Xu, Zhu and Meng Materials and Corrosion 2014, 65, No. 11

Figure 2. Microscopic morphologies of 13Cr stainless steel samples after different test durations after corrosion test: (a) 7 days; (b) 15 days; (c) 30 days;
(d) 60 days

Table 3. EDS results in zone A shown in Fig. 2a, wt% Table 4. EDS results in zone B shown in Fig. 2a, wt%

O Br P K Cr Fe O Br P K Cr Fe

11.25 0.52 0.50 0.16 17.04 70.52 26.50 31.87 8.49 7.46 8.10 17.58

showed that a considerable amount of element Br, K, and P were
traced (Table 4). After the exposure of 15 days, the salt particles
became bigger, but were still discrete, as shown in Fig. 2b. After
the exposure of 30 days, more salt particles deposited on the
passive film. Figure 2d showed that specimen surface had been
covered by a compact salt film at 60 days.
Figure 3 indicated the macroscopic morphologies of the
specimens after the removal of the corrosion product. Figure 3a–d
revealed that there were no obvious pits on the steel surface from
the macroscopic morphologies.
However, pitting corrosion appeared on the 13Cr steel
surface for long corrosion periods (30 and 60 days) by microscopic
observation after the removal of the corrosion products. As shown
in Fig. 4a, localized corrosion was not found on the surface of the
samples after the exposure of 7 days. After the exposure of
15 days, tiny pits appeared on the sample surface, the size of the

Figure 3. Macroscopic morphologies of 13Cr stainless steel samples after different test durations after the removal of the corrosion products:
(a) 7 days; (b) 15 days; (c) 30 days; (d) 60 days

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Materials and Corrosion 2014, 65, No. 11 Pitting corrosion of 13Cr steel 1099

Figure 4. Microscopic morphologies of 13Cr stainless steel samples after different test durations after the removal of the corrosion products:
(a) 7 days; (b) 15 days; (c) 30 days; (d) 60 days

pits is around 1–2 µm in diameter as shown in Fig. 4b, which
demonstrated the speed of pitting nucleation was relatively slow.
For longer exposure time (30 and 60 days), some pits appeared.
Small pits with 4–5 µm in diameter were observed on the
specimen surface, as shown in Fig. 4c. Figure 4d showed there
were many pits with 7–8 µm in diameter on the sample surface. It
was clear that the size and number of pits gradually increased
with the corrosion time, as shown in Fig. 4c and d.
In order to further understand the development of the pits,
the cross‐sectional view of the corrosion product film was
investigated after different corrosion time. Figure 5 shows the
electron back scattering diffraction (EBSD) images of the pits. As
exhibited in the figures, different size and shape of the pits were
induced in brine completion fluids after different test durations.
Apparently, pitting corrosion had not been found on the surface of
the samples after the exposure of 7 days. The metal substrate

Figure 5. Cross‐sectional morphologies of 13Cr stainless steels after corrosion test after different test durations: (a) 7 days; (b) 15 days; (c) 30 days;
(d) 60 days

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1100 Liu, Xu, Zhu and Meng
Figure 6. EDS analysis results of product inside the pits from Fig. 5: (a) pit A; (b) pit B; (c) pit C
surface was a little bit fluctuated after corrosion, as shown in
Fig. 5a. With longer corrosion time, some pits which were filled
with corrosion product were observed, as shown in Fig. 5b–d.
EDS was used to analyze the composition of corrosion product in
the pits, and the results were shown in Fig. 6. As exhibited in
Fig. 5b, the pit A looked like a narrow cone with 3 µm in depth.
Figure 6a showed the filler of the pit mainly contained Fe, Cr, O,
and Br. It was worth noticing the presence of considerable
amount of Br in the filler. Then several pan‐like pits appeared on
the sample surface after the exposure of 30 days, as shown in
Fig. 5c. And the pit B was about 4 µm in depth. The composition
of filler of pit B was also analyzed by EDS. The content of Fe, Cr, K,
and P of the product inside pit B increased in comparison with
that in pit A, as shown in Fig. 6b. At the exposure of 60 days, a
layer of dense salt film around 2–3 µm covered the surface of the
substrate and a typical V shape pit with 6–7 µm was present, as
shown in Fig. 5d. The pitting corrosion rate is about 0.04 mm/
year. The composition of pit C was investigated by EDS analysis,
as shown in Fig. 6c. The result showed that the Cr in pit C
increased a little bit more than the Cr in pit B.
4 Discussion
The results show that the surface of 13Cr stainless steel revealed
pitting corrosion in this test condition. According to literature
[19–22], the generation of pitting corrosion is mainly related to
passivation of stainless steel. The pH values of the corrosion
solution, measured under normal temperature and pressure
before the experiment, are listed in Table 5. It can be seen that
the pH values of salt solution under various test durations are all
>7, indicating the solutions are alkaline. Moreover, the partial
pressure of oxygen is 0.53 MPa in the experiment. Some
Table 5. pH values before and after corrosion test in the salt solution
after different test durations
Test duration Before corrosion After corrosion
(days) test test
7 10.85 10.46
15 10.89 10.31
30 10.93 10.44
60 10.81 10.54
© 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Materials and Corrosion 2014, 65, No. 11
literature [17,18] pointed out that the stainless steel is susceptible
to being passivated in the presence of O2 or under the exposure of
alkaline solution. That means the passive film, i.e. a thin oxide
layer, is easy to form under the test condition. And then the
presence of the passive film on the steel surface will greatly reduce
the rate of corrosion of the metals. However, once the protective
passive film is damaged somewhere, fresh metal substrate will be
exposed in aggressive corrosion environment. Then the dissolu-
tion of the underlying metal is accelerated, resulting in pitting
corrosion.
Consequently, according to the literature [23–25] we consider
the corrosion process of the experiment proceeded mainly in
accordance with the following equations:
1st step: Pitting nucleation
1
Fe þ O2 þ H2 O ! Fe2þ þ 2OH
ð1Þ
2
3 3
Cr þ O2 þ H2 O ! Cr3þ þ 3OH
ð2Þ
4 2
2nd step: Pitting growth
Fe2þ þ 2Br
þ 2H2 O ! FeðOHÞ2 þ 2HBr ð3Þ
3rd step: Corrosion product formation
1
3FeðOHÞ2 þ O2 ! Fe3 O4 þ 3H2 O ð4Þ
2
However, the pitting corrosion process is so complicated that
controversies relating to the pitting mechanisms occur. For this
work, the schematic picture (Fig. 7) is proposed to describe the
evolution of pitting corrosion in the Br
containing salt solution
at the case of high temperature and pressure. Then a passive film
is easily formed on the metal surface in the aerated Br

containing simulation solution, as shown in Fig. 7b. According to
the literature [26], the passivated film on the 13% Cr steel surface
is always thin, probably about 20 nm. Figure 7c describes that the
salt particles gradually deposit onto the surface of the passive film,
which may be caused by the super‐saturation of the salt in the
solution. According to the literature [27], aggressive Br
in salt
particles first forced to exchange oxygen from the oxide film, and
then soluble FeBr2 generates, resulting in the damage of the
passive film. Then Br
is directly contacted to the fresh substrate
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Materials and Corrosion 2014, 65, No. 11 Pitting corrosion of 13Cr steel 1101

Figure 7. Schematic diagrams of the mechanism of pits development: (a) the initial sample placed in the solution; (b) the formation of passive film;
(c) deposition of organic salt particles; (d) breakdown of passive film; (e) growth of pits; (f) the filling of salt inside the pit

at the place where the passive film is broken. That will result in
acceleration of localized corrosion. As a result, a small stable pit
gradually grows with time (Fig. 7d).
Simultaneously, more Br
and other ions (Kþ, PO3
4 )
migrate into the pits. The pits filled with more Br
will continue
to grow, while other pits may stop developing due to the
repassivation of the substrate. As shown in Fig. 6b, the deep and
narrow pit was filled with a large number of Br
after 15 days of
test time, which demonstrates that Br
involves in the expansion
of the pits. So the growth of the pit is accompanied with the filling
of salt (Fig. 7e), and Br
may participate in the corrosion process
as shown in Equation (3). Thus the contact interfaces of the salts
and substrate in the pit maintain an activated state and become
more difficult to repassivate. As a result, the pit will continue to
expand. More salts move into the pit with the expansion of the pit,
as shown in Fig. 7f.
Figure 6 shows that the composition of fillers in the pits
gradually changed, which can be explained by Fig. 8. Bromine ion
is an anion of strong acid with a high diffusivity, and it interferes
with passivation. Therefore most of fillers in the pits are Br
at the
beginning stage, as shown in Fig. 8a. The enrichment of Br
will
lead to charge imbalance in the pits. In order to maintain charge
neutrality, cations such as Kþ in the salt solution are gradually
sucked into the pit under the electric field, as shown in Fig. 8b.

Figure 8. Schematic diagrams of the migration of ions in the pit

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1102 Liu, Xu, Zhu and Meng
With the extension of corrosion time, more and more corrosion
products generate in the pits following Equation (4), which
decreases the direct contact of the salts and the substrate, as
shown in Fig. 8c.
5 Conclusions
The pitting corrosion of 13Cr steel in aerated Br
containing
brine completion fluids has been investigated, and the results
have been concluded as following:
1. In aerated salt solution containing Br
with high temperature
and high pressure (150 8C, 3 MPa), the 13Cr steel is
susceptible to slight pitting corrosion. At the test of 60 days,
the rate of pitting corrosion is about 0.04 mm/year, and the
average general corrosion rate is 0.01 mm/year.
2. For short period of corrosion (7 days), there was no pit on the
13Cr surface. Very small pits occurred at 15 days, and the pits
were filled with salt. For long periods of corrosion (30 and
60 days), the pits grew up slowly and the composition of the
filler had changed slightly.
3. At the early stage of pitting growth, the main component of
the filler is Br. It is deduced that Br
involved in both the
breakdown of the passive film and the expansion of the pits.
Acknowledgments: The authors are grateful for the support
of the National Science & Technology Pillar Program (Grant No.
2012BAK13B04).
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(Received: November 1, 2013) W7489
(Accepted: December 2, 2013)
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