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Corrosion Science: Pengpeng Bai, Shuqi Zheng, Hui Zhao, Yu Ding, Jian Wu, Changfeng Chen

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Corrosion Science 87 (2014) 397–406

Contents lists available at ScienceDirect

Corrosion Science
journal homepage: www.elsevier.com/locate/corsci

Investigations of the diverse corrosion products on steel in a hydrogen


sulfide environment
Pengpeng Bai, Shuqi Zheng ⇑, Hui Zhao, Yu Ding, Jian Wu, Changfeng Chen
State Key Laboratory of Heavy Oil Processing and Department of Materials Science and Engineering, China University of Petroleum, Beijing 102249, PR China

a r t i c l e i n f o a b s t r a c t

Article history: The corrosion products of carbon steel in aqueous H2S environment are investigated. The products, which
Received 21 December 2013 include mackinawite, cubic FeS, troilite, and pyrite, are characterized through their shapes, chemical
Accepted 30 June 2014 compositions and crystal structures. Mackinawite appears with a flake shape. Cubic FeS has a perfect/
Available online 8 July 2014
truncated octahedral shape, and pyrite is framboid-shaped. Flower-shaped troilite is developed from
beam- or hexagonal wire-shaped grains by electrostatic interactions along a certain lattice plane. The
Keywords: large single beam-shaped troilite has a growth pattern along the c axis. The corresponding crystal struc-
A. Carbon steel
ture and micro-morphology of the corrosion products are provided, and the three-dimensional models of
B. SEM
B. TEM
them are generated.
C. Acid corrosion Ó 2014 Elsevier Ltd. All rights reserved.
C. Sulphidation

1. Introduction the past several years has led to the synthesis of numerous
iron–sulfur compounds [12–15].
Hydrogen sulfide (H2S) corrosion, especially sulfide-stress Steel corrosion products in H2S environment are complex and
cracking (SSC) and hydrogen-induced cracking (HIC), has long indistinguishable. Minor changes in test conditions can lead to
attracted much attention because high H2S concentrations can diverse results. Corrosion products under various conditions have
lead to pitting, localized corrosion, and failures [1–3]. H2S is been characterized in numerous studies. Tetragonal iron sulfide
formed in organically enriched sediments via the reduction of has been determined as the initial product of iron in H2S solu-
sulfate ions induced by sulfate-reducing bacteria, and this com- tions [16]. The evolution of products on discs progresses from
pound exists in benthic ecosystems, oil and gas systems, and iron-rich to sulfide-rich phases in oxygen-free solutions under
sewage [4,5]. Corrosion product films should be characterized 1 MPa pressure [17]. Mackinawite is formed by both solid-state
to determine the corrosion mechanism and is significant in the and precipitation processes, whereas cubic FeS and troilite are
development of new corrosion inhibitors. Corrosion products the subsequent phases on an iron surface exposed to saturated
have been proven to modify steel damage in certain cases and aqueous H2S at 21 °C and pH 4 [18]. Multilayer corrosion product
resemble passive stainless steel films [6–9]. Corrosion products films have been investigated in a CO2/H2S environment, and iron
of iron or steel in aqueous H2S environment produce iron–sulfur sulfide films have been found to cause a substantial rate reduc-
compounds with various phases and play a key role in the envi- tion [19]. Mackinawite cracking leads to the nucleation of other
ronment. Geologists, physicists, chemists, biologists, and material types of iron sulfides [20].
scientists have expressed keen interest in the iron–sulfur system, Varying corrosion products under different conditions have
and related studies can be traced back to the last century or been reported. However, detailed studies on the microstructures
even earlier [10]. Different solids that comprise only iron and of these products are insufficient. The authors have previously
sulfur originating from the formation of different stoichiometric shown through in situ electrochemical techniques that hexagonal
ratios have been identified. These solids include mackinawite iron sulfides decrease the steady state hydrogen flux in steel
(FeS), cubic FeS, troilite (FeS), pyrrhotite (Fe1xS), smythite [21]. In the present study, the morphological characteristics, chem-
(Fe9S11), greigite (Fe3S4), pyrite (FeS2), and marcasite (FeS2) ical compositions, and crystal structures of various corrosion prod-
[11]. The rapid development in science and technology during ucts of iron in H2S environment are investigated. The
corresponding crystal structures and micro-morphologies are
determined, and the corrosion products are examined using scan-
⇑ Corresponding author. ning electron microscopy (SEM), X-ray diffraction (XRD), and
E-mail addresses: zhengsq09@163.com, zhengsq@cup.edu.cn (S. Zheng). transmission electron microscopy (TEM).

http://dx.doi.org/10.1016/j.corsci.2014.06.048
0010-938X/Ó 2014 Elsevier Ltd. All rights reserved.
398 P. Bai et al. / Corrosion Science 87 (2014) 397–406

2. Experimental procedure micrographs were taken with an FEI Quanta 200F scanning elec-
tron microscope. The crystal structures of the corrosion products
2.1. Materials and sample preparation were characterized by a Bruker AXS XRD-D8 Focus X-ray diffrac-
tometer. Scanning transmission electron microscopy–energy
Commercial X52 pipeline steel with typical ferrite and pearlite dispersive X-ray (STEM–EDX) images, selected area electron
microstructure was used as the experimental material. The steel diffraction (SAED) patterns, and high-resolution transmission elec-
chemical composition (wt%) was as follows: C, 0.13; Si, 0.4; Mn, tron microscopy (HRTEM) images were recorded on an FEI F20
1.5; P, 0.02; S, 0.003; Cr, 0.3; and Fe balance. The specimen was field-emission transmission electron microscope with an accelera-
machined to a disc with 3 mm thickness and 30 mm outer diame- tion voltage of 200 kV.
ter. Prior to each experiment, the specimen was ground with 400
grit to 1500 grit silicon carbide paper and water until a homoge- 3. Results and discussion
neous surface was obtained. The specimen was then degreased
with acetone, thoroughly rinsed with distilled water, and quickly The established reactions between iron and H2S are as follows
dried using cold air to avoid oxidation. The specimen was embed- [22]:
ded in a Teflon base fixture until further testing.
Anodic reaction :Fe ! Fe2þ þ 2e ð1Þ
þ 
2.2. Corrosion product film deposition H2 S dissociation reactions :H2 S ! H þ HS ð2Þ
HS ! Hþ þ S2 ð3Þ
Table 1 shows the test conditions. Three experiments were per-  2
Cathodic reaction :H2 SðaqÞ þ 2e ! H2 þ S ð4Þ
formed to study the effects of pressure, temperature, and reaction
time on the properties of the corrosion products. Overall reaction :Fe þ H2 SðaqÞ ! FeS þ H2 ð5Þ
Tests were performed at 0.1 MPa in a facility that satisfied the The authors have previously shown that corrosion products
test requirements (Fig. 1). The solution was poured into a vessel change with different reaction times of iron and H2S, and these
and deoxygenated prior to the tests. The solution was saturated changes affect subsequent reactions [21,23]. In the authors’ studies
with H2S at a rate of at least 100 mL/min for 1 h. H2S gas was bub- on the growth and conversion of products under different condi-
bled through the test solution. tions, the sequence of the corrosion products has been elucidated.
Tests above 0.1 MPa were performed in an autoclave (70 MPa) A systematic study has been conducted to completely characterize
made by Cortest Company. Prior to the test, the autoclave was the products.
deaerated for 12 h using high purity N2. The system was then pres-
surized with H2S at 1 MPa according to the test requirements. The
3.1. Characteristic of corrosion products
experiment was initiated when the required test conditions were
met. All tests were performed at 50 °C for 6, 12, 18, 24, 48, 72,
3.1.1. Corrosion product films in the vapor phase
and 96 h. After the tests, the specimens were removed from the
Steel in H2S gas environments may corrode more significantly
autoclave, rinsed with distilled water and absolute alcohol, and
compared with that in H2S in aqueous brine solutions, particularly
air-dried.
in the oil–gas field. The types of corrosion products generated are
related to factors such as temperature and pressure. Previous
2.3. Morphological characterization of corrosion products reports have shown that corrosion products consist of pyrite, troi-
lite, and mackinawite below 4 Pisa H2S [24]. Pyrrhotite is the major
The corrosion product films were characterized by SEM, XRD corrosion product of 4130 alloy in gaseous environment that con-
and TEM. SEM-energy dispersive X-ray spectroscopy (SEM-EDS) tains 10% H2S in argon at 204 °C [25]. The corrosion behavior of

Table 1
Experimental conditions.

Condition no. Pressure of H2S (MPa) Temperature (°C) Period (h) Medium
1 0.1 90 0.5, 2, 4, 24, 48, 72, 168 Vapor
2 0.1 25, 50, 75, 99 168 5% NaCl solution
3 1 50 6, 12, 18, 21, 24, 48, 72 Distilled water

Fig. 1. Schematic diagram of corrosion product films deposition at 0.1 MPa.


P. Bai et al. / Corrosion Science 87 (2014) 397–406 399

steel has been intensively investigated in gaseous H2S environment


under diverse experimental conditions. However, most of these
studies are performed at high temperatures, even reaching
900 °C, and the gaseous environment always contains other gases,
such as CO2 and sulfur vapor [26,27]. Experiments with much
lower temperature have been considered because the real temper-
atures of some oil and gas pipelines are below 100 °C. Therefore,
the experimental conditions in this study differ from previous
studies. A relatively low temperature (90 °C) closer to real condi-
tions is chosen, and a pure H2S environment, instead of a gas mix-
ture such as CO2 or H2 is implemented. The corrosion products that
form during the vapor phase at 90 °C are investigated.
Fig. 2 shows the SEM micrograph of the corrosion product films
that form in the H2S–H2O vapor phase at 90 °C under different
reaction times. Fig. 3 shows the corresponding XRD patterns. The
XRD pattern shows that troilite and cubic FeS are the main phases
after 24 h reaction, and troilite is the only phase after 72 h reaction.
No pyrrhotite or pyrite is observed. The SEM image shows that the
corrosion products undergo rapid nucleation, and the surface of the
steel was covered with nanocrystals, which are the initial products Fig. 3. XRD patterns of corrosion product films formed in H2S–H2O vapor phase at
after 0.5 h reaction (Fig. 2a). Fig. 2c–f shows that beam-shaped and 90 °C at 2, 24, and 72 h.
fest products appears after 4 h reaction and the beam-shaped
products become the main phase after 24 h. Given that the prod- current data, in which beam-shaped troilite has been found to be
ucts seldom appear until 24 h, the structural date of the nanocrys- the main phase. Troilite belongs to the pyrrhotite system and has
tal products are not obtained. The XRD pattern only shows Fe at a NiAs-type 2C superstructure. This compound has been found to
2 h, and troilite is the main phase after 24 h reaction. Mackinawite undergo a spin-flip transition (a-transition) at 140 °C and a first-
is the initial crystalline product of steel in an H2S environment, so order transition (b-transition) to the NiAs subcell (1C) at 315 °C
the nanocrystal products most likely develop to mackinawite and [28]. Therefore, the authors deduce that troilite is the main phase
cubic FeS, and they disappear subsequently because of the excess in H2S environment at environmental temperatures below 140 °C
sulfur from the dissolved H2S. The limited growth of hexagonal because of the instability of troilite at high temperature, and pyr-
iron sulfide (pyrrhotite and troilite) has been discussed for almost rhotite appears at environment temperatures above 140 °C in most
40 years. The most acceptable theory is that hexagonal iron sulfide cases.
forms by the predominant outward motion of iron ions through the
iron-sulfide film. The discovery of layered corrosion products pro- 3.1.2. Characteristic of corrosion product films in aqueous H2S brine
vides evidence for this theory [25]. solution under atmospheric pressure
Results from the present study differ from those found in the In oil and gas fields, chloride from the dissolved salts in the wild
literature. Numerous studies have demonstrated that pyrrhotite is always found in the aqueous environment and serves as a cata-
is the main phase in an H2S gas environment, contrary to the lyst for the CO2/H2S corrosion of steel [29]. Hence, aqueous H2S

Fig. 2. SEM micrographs of corrosion product films formed during the H2S–H2O vapor phase at 90 °C under different reaction times: (a) 0.5, (b) 2, (c) 4, (d) 24, (e) 48, and (f)
72 h.
400 P. Bai et al. / Corrosion Science 87 (2014) 397–406

brine solution is chosen as the corrosion medium in the current


study. Temperature is another important factor in corrosion behav-
ior. In a previous study by the authors, the corrosion rate of
A350LF2 has been found to initially increase and subsequently
decrease significantly with increasing temperature from 25 °C to
90 °C [30]. Mackinawite is easily separated from an alcohol base
through ultrasonic washing because it is the main product of steel
corrosion in an aqueous H2S environment under atmospheric pres-
sure [21]. In the current study, the corrosion products on carbon
steel are investigated in aqueous H2S brine solution at 25 °C,
50 °C, 75 °C, and 99 °C. Fig. 4 shows the SEM micrograph of the cor-
rosion products in the aqueous H2S brine solution under atmo-
spheric pressure at different temperatures after 168 h reaction.
Fig. 5 shows the corresponding XRD patterns. The XRD patterns
show that mackinawite was the only product that forms at various
temperatures in aqueous H2S brine solution under atmospheric
pressure after 168 h reaction. No troilite, pyrrhotite, or pyrite been
is found (Fig. 5). The corrosion products on steel at 25 °C consist
mainly of nanocrystals (Fig. 2a), which can be considered as one
of the shapes of mackinawite. By contrast, flake-shaped grains Fig. 5. XRD patterns of corrosion product films formed in aqueous H2S brine
are the main products on steel at 50 °C, 75 °C, and 99 °C (Fig. 2b), solution under atmospheric pressure at different temperatures for 168 h.

and the size of flake-shaped corrosion products on steel at 50 °C


are smaller than those at 75 °C and 99 °C (Fig. 2c and d). The factors
for the occurrence of mackinawite as the only corrosion product
ion in the solution from forming mackinawite. However, corrosion
under the given conditions are complex. First, iron dissolves in
product films have self-repair capabilities and become increasingly
an acid solution (the pH is about 4 in this condition). Consequently,
stable as their thickness increases [32]. Thus, the development
iron ions are more abundant than sulfur ions, so an iron-rich prod-
of stable hexagonal phases (troilite and pyrrhotite) can be
uct, similar to mackinawite, can be the main phase. However, pre-
slowed down because of the damage to the substrate caused by
vious reports have shown that diverse iron sulfide products, not
chloride.
only iron-rich mackinawite, can be found in the pH range from 4
to 6.3 in an aqueous H2S solution [31]. Therefore, pH is not the only
factor to be considered. Second, the stable hexagonal phases (troi- 3.1.3. Characteristic of corrosion product films in aqueous H2S solution
lite and pyrrhotite) grow outside the iron-rich product films with 1 MPa pressure
because unbroken corrosion product films prevent the diffusion Corrosion products undergo rapid nucleation and growth, and
of iron ion toward the solid–liquid interface. Both the steel base the steel surface is covered with various shapes of incomplete
and corrosion product films may be destroyed by the chloride in compounds (e.g., nanocrystals, flake-shaped, and irregular blocks)
aqueous H2S solution, and the damaged films cannot stop the iron after 6 h reaction (Fig. 6a). The steel is covered with the most num-
ber of compounds (Fig. 6b), particularly with a mass of an irregular
block, after 12 h. Some small flake-shaped and incomplete octahe-
dral compounds are evident. This stage is considered as the first
reaction period until 12 h. Fig. 7 shows that the main phases are
mackinawite and cubic FeS. Beam- and hexagonal wire-shaped
compounds appear after 18 h (Fig. 6c). Flower-like compounds
cover most of the steel surface after 24 h (Fig. 6d–f). The interme-
diate state of the flower-shaped compound demonstrates a forma-
tion mechanism. Fig. 8a shows that flower-like iron sulfide appears
at the 18 h period. ‘‘I’’ indicates a single beam-shaped crystal, ‘‘II’’
indicates several beam-shaped grains united along a certain lattice
plane, and ‘‘III’’ indicates several Fe–S particles adsorbed on the
interface of the beam-shaped grains through electrostatic interac-
tions. The three-step growth of the flower-like compounds can be
described as follows. First, beam- or hexagonal wire-shaped
compounds nucleate by solid-state phase transition or chemical
reaction. Thereafter, individual beams or hexagonal wires fuse
together. The interface of the distinct crystals adsorbs the iron–sul-
fur particles, and electrostatic interactions play an important role
in this step. Units of different crystals form along a perfect lattice
match [33]. Fig. 8b shows that the character of the transition-state
troilite exhibits many defects in the flower. Many rough edges on
the interface of various crystals are evident during this period. A
perfect flower-like compound emerges as the final phase (Fig. 8c)
and the final shape is most likely related to Gibbs free energy. This
stage is considered as the second period after 12 h, and the main
Fig. 4. SEM micrographs of corrosion product films formed in aqueous H2S brine
phases are identified as troilite by XRD. Hence, the sequence of
solution under atmospheric pressure at different temperatures for 168 h. (a) 25 °C, the main corrosion products is determined as mackinawite + cubic
(b) 50 °C, (c) 75 °C, and (d) 99 °C. FeS ? troilite in this scenario.
P. Bai et al. / Corrosion Science 87 (2014) 397–406 401

Fig. 6. SEM micrographs of corrosion product films at 50 °C with 1 MPa H2S at different reaction times: (a) 6, (b) 12, (c) 18, (d) 21, (e) 24, and (f) 72 h. The corrosion products
are complex. M, C, and T stand for mackinawite, cubic FeS, and troilite, respectively.

3.2. Chemical compositions and crystal structures of corrosion


products

3.2.1. Chemical compositions of corrosion products


Fig. 9 shows the SEM-EDS micrographs of the different corro-
sion products. Table 2 shows the elemental percentage in Fig. 9
obtained by EDS. The nanocrystal products in the H2S vapor envi-
ronment at 0.5 h are determined as a type of iron-sulfide com-
pound (Fig. 9a and b). Similarly shaped nanocrystal products
have been found in other studies [34], but these products are pure
iron-sulfide compounds. In the current study, all tests are per-
formed in an oxygen-free environment, so the nanocrystal is cer-
tainly a type of iron-sulfide compound. Nevertheless, the crystal
structure cannot be determined because the nanocrystal is tightly
wired together with the iron base and cannot be separated for TEM
analysis. Octahedral and beam-shaped products are common in the
H2S environment. The EDS micrographs show that these products
are probably monosulfides given the mini deviation (Fig. 9c–f).
Fig. 9h shows the EDS of framboidal products obtained at the
48 h period with 1 MPa H2S. These products are not the main
Fig. 7. XRD patterns of corrosion product films at 50 °C with 1 MPa H2S at different phase, but few grains are distributed randomly around the
reaction times. flower-shaped products. The framboidal products are assumed to
be disulfides.
Fig. 10 shows the STEM-EDX micrographs of nanowires
In this test, a special clear aqueous environment containing only
obtained at the 96 h period with 1 MPa H2S. Nanowires are uncom-
H2S is chosen to study the corrosion products. Result shows that
mon in the present study, and the nanowire diameter is approxi-
both the crystal structure and microtopography rapidly change
mately 20 nm (Fig. 10a and b). The ratio of Fe and S is
with the reaction time. The SEM micrographs show that the shapes
approximately 1:1. The EDX mapping result shows that the Fe-
of the products change from nanoparticle and block to beam shape
to-S ratio is above 1:1. This result may have been caused by the
and then to flower-like appearance. Stable corrosion products form
Fe enrichment around the surface of the nanowire (Fig. 10d).
more quickly and earlier compared with those under other condi-
tions. This phenomenon may have been caused by two factors. One
is the presence of excess sulfur ion in the test solution under 1 MPa 3.2.2. Crystal structures of corrosion products
H2S pressure. The other is that the steel and corrosion product TEM was used to study the crystal structures of the corrosion
films are not damaged by other factors, such as CO2 and chloride, products. The TEM sample is selected among the products obtained
therefore iron dissolution is reduced. These conditions result in at 18 h under condition 3 (Table 1). Various types of iron sulfides
more efficient growth of sulfur-rich products. are found to coexist based on the XRD obtained for this period.
402 P. Bai et al. / Corrosion Science 87 (2014) 397–406

Fig. 8. SEM micrographs of flower-like corrosion products. (a) The growing flower-like iron sulfide (troilite) appeared at the 18 h period. (b) Intermediate-state flower-like
iron sulfide (troilite) appeared at the 21 h period. (c) Perfect flower-like iron sulfide (troilite) appeared at the 24 h period.

Fig. 9. SEM–EDS micrographs of corrosion products formed in the H2S environment. (a) SEM micrograph of nanocrystal products formed in the H2S vapor environment. (b)
EDS spectra of nanocrystal products; (c) SEM micrograph of octahedron-shaped products obtained at the 12 h period with 1 MPa H2S; (d) EDS spectra of octahedron-shaped
products; (e) SEM micrograph of beam-shaped products obtained at the 21 h period with 1 MPa H2S; (f) EDS spectra of beam-shaped products; (g) SEM micrograph of
framboidal-shaped products obtained at the 48 h period with 1 MPa H2S; and (h) EDS spectra of framboidal-shaped products.

Table 2
Percentage of elements obtained by EDS. Mackinawite has received considerable attention in different
Element (at%) Fe S C Mn Si fields [35]. It possesses a tetragonal layered structure in which Fe
atoms are linked in a tetrahedral coordination to four equidistant
Fig. 4a 83.87 07.45 06.23 01.59 0.86
Fig. 4c 43.99 47.43 08.58 0 0 sulfur atoms [36]. The crystal structure is identified by SAED pat-
Fig. 4e 39.19 44.44 15.25 0 0 terns (Fig. 11b). The SAED patterns are intended to be the [0 0 1]
Fig. 4g 25.56 50.66 23.78 0 0 of mackinawite. Mackinawite is converted to pyrrhotite by heating
between 530 K and 545 K [37]. The disappearance of mackinawite
Fig. 11 shows the SAED patterns of the flake-shaped and octahedral with the appearance of cubic FeS and troilite is probably caused by
products determined as mackinawite and cubic FeS, respectively. phase transformation, although this process is not observed.
P. Bai et al. / Corrosion Science 87 (2014) 397–406 403

troilite in various types of minerals has been previously investi-


gated.
pffiffiffiTroilite has an NiAs-type superstructure with a unit cell of
a ¼ 3 A and c = 2C (where A and C refer to an NiAs-type structure)
at room temperature; this phase is generally called low-tempera-
ture troilite [41]. In addition to its low-temperature NiAs-type
structure, a different crystal structure of troilite is found from the
lunar sample 10,050 (high-temperature structure) [42]. Synthetic
troilite with an MnP-type structure is prepared under high-pres-
sure and high-temperature conditions [43]. Although numerous
studies have shown the structural characteristics of troilite in nat-
ure, no detailed report has been published on troilite as a product
of the reaction between iron and H2S. The crystal structure of troi-
lite is identified through SAED patterns, and the corresponding
HRTEM from a beam-shaped grain is obtained (Fig. 12). Based on
the SAED patterns, the beam-shaped troilite is determined to have
a growth pattern along the c axis and a low-temperature structure
that is stable below 140 °C. Relative to other synthetic iron sulfides,
the single beam-shaped crystal is large and both of the phase-con-
trast images reveal planar defects that are predominantly stacking
faults, which are particularly perpendicular to the c axis (Fig. 12b).
The phase contrast also demonstrates a perfect crystalline order,
most likely because troilite is thermodynamically more stable than
other phases [44]. Troilite should be more stable than cubic FeS or
mackinawite because it is the last main phase in the whole reac-
Fig. 10. STEM–EDX micrographs of nanowires. tion of iron and H2S.

3.3. Microtopography of the corrosion products

The study results show that the main corrosion products are
mackinawite, cubic FeS, and troilite. Few pyrite grains are also
found in the products at the 18 h period under condition 3 in
Table 1. Fig. 13 shows the SEM micrographs and corresponding
three-dimensional (3D) models of the products. Steel and H2S
products are diverse and are formed not only during crystal growth
but also during phase transition. The different phases are highly
distinct from one another.
Mackinawite, which is the first product in the H2S environment
according to our observation, mainly appears as flake-shaped or
irregular blocks. Mackinawite has other morphologies that are
not observed. Fig. 13c shows the SEM of flake-shaped mackinawite
obtained under condition 2 in Table 1. Fig. 13d shows the 3D model
of flake-shaped mackinawite. Mackinawite is an important product
of steel in H2S environment, especially in aqueous H2S solution
under atmospheric pressure. Tewari et al. studied the dissolution
rate of diverse iron sulfide compounds and indicated that the dis-
solution rate of mackinawite is about 20 times faster than that of
troilite and 1000 times faster than those of pyrite and pyrrhotite
[45]. They also inferred that the corrosion behavior of steel is con-
trolled by the dissolution rate of mackinawite in H2S environment
[45]. Although the dissolution rate of mackinawite cannot be
affirmed as the only factor needed to elucidate the corrosion mech-
Fig. 11. SAED patterns of iron–sulfur compounds. (a) Low-magnification image
showing the flake-shaped crystal; (b) SAED pattern corresponding to [0 0 1] of the
anism, mackinawite always plays a key role in H2S corrosion.
mackinawite; (c) low-magnification image showing the octahedron-shaped fest; Cubic FeS is not found naturally because it mainly forms as a
and (d) SAED pattern corresponding to [1 0 0] of the cubic FeS. product of the reaction of Fe with H2S. Cubic FeS was first identi-
fied by de Medicis as a metastable phase [46]. Perfect cubic FeS
crystals are formed at 50 °C and pH 4 to pH 5 [18]. Murowchick
Limited studies have been performed on cubic FeS, which has a showed that cubic FeS is formed by the reactions between aqueous
sphalerite structure [38], caused by its unstable characteristic com- H2S and Fe [47]. In the current study, cubic FeS mainly appears as
pared with other phases. Cubic FeS is mainly found in magnetotac- 3 lm-wide perfect/truncated octahedrons (Fig. 13c). Fig. 13d
tic bacteria in recent years [39]. Although cubic FeS is not naturally shows the 3D model of the perfect octahedron.
found, it is worthy of further investigation because this phase can Pyrite is the most common natural sulfide mineral in surface
be a precursor to mackinawite or other products [40]. The crystal environments. Pyrite is well-known to be of a cubic structure
structure of cubic FeS is identified by SAED patterns (Fig. 11d). [39,48]. Pyrite has been synthesized by the reaction of dissolved
The SAED patterns can be considered the [1 0 0] of cubic FeS. iron, H2S, and elemental sulfur in the laboratory [49]. Shoesmith
Fig. 12 shows the HRTEM images and SAED patterns of the obtained pyrite on the surface of stainless steel by electrocrystalli-
beam-shaped iron sulfide determined as troilite. The structure of zation and found that pyrite formation is easier under excessive
404 P. Bai et al. / Corrosion Science 87 (2014) 397–406

Fig. 12. HRTEM micrographs and SAED patterns in two different zone axes of the beam-shaped iron sulfide (troilite); (a) low-magnification image showing the beam-shaped
8 lm-long grain; (b and c) HRTEM micrographs corresponding to [1 0 0] and [1 1 0] of the troilite, respectively; (b) HRTEM image showing planar defects (stacking faults)
along the c axis; and (d and e) SAED patterns along two different zone axes may be the [1 0 0] and [1 1 0] of troilite, respectively.

Fig. 13. Summary of the SEM and 3D models of the corrosion products. (a) SEM micrograph and (b) 3D model of the flake-shaped mackinawite obtained at the 6 h period; (c)
SEM micrograph and (d) 3D model of the octahedron-shaped cubic fest obtained at the 12 h period; (e) SEM micrograph and (f) 3D model of the framboidal-shaped pyrite
obtained at the 48 h period; SEM micrograph of (g) beam-shaped troilite obtained at the 18 h period and (i) hexagonal wire-shaped troilite obtained at the 21 h period; (h) 3D
model corresponding to (g) and (i).

ferrous ion condition [50]. In the current study, very few pyrite Pyrrhotite is the most abundant iron sulfide in nature. Consid-
products are found, and the micromorphology of pyrite is framboi- ered one of the most common products in H2S environments, pyr-
dal (Fig. 13e). Fig. 13f shows the 3D model. rhotite has many natural superstructures [11]. Wikjord et al.
P. Bai et al. / Corrosion Science 87 (2014) 397–406 405

observed that pyrrhotite appears as hexagonal platelets in carbon [10] J.W. Morse, F.J. Millero, J.C. Cornwell, D. Rickard, The chemistry of the
hydrogen sulfide and iron sulfide systems in natural waters, Earth-Sci. Rev. 24
steel by H2S under 1.5 MPa pressures [16]. In the present study,
(1987) 1–42.
pyrrhotite 2C (troilite) is the final reaction product in tests 1 and [11] D. Rickard, G.W. Luther, Chemistry of iron sulfides, Chem. Rev. 107 (2007)
3. Although products in H2S environments are limited, and that 514–562.
the microtopography of troilite is needle-like [20], no report has [12] T. Douglas, D.P.E. Dickson, S. Betteridge, J. Charnock, C.D. Garner, S. Mann,
Synthesis and structure of an iron(III) sulfide–ferritin bioinorganic
provided a detailed description of troilite. Troilites appear as beam nanocomposite, Science 269 (1995) 54–57.
or hexagonal wires with lengths between 10 lm and 50 lm during [13] P.V. Vanitha, P. O’Brien, Phase control in the synthesis of magnetic iron sulfide
the early reaction period. These troilite wires then develop into nanocrystals from a cubane-type Fe–S cluster, J. Am. Chem. Soc. 130 (2008)
17256–17257.
flower-like structures with diameters of approximately 100 lm [14] D.R. Cummins, H.B. Russell, J.B. Jasinski, M. Menon, M.K. Sunkara, Iron sulfide
(Fig. 13g and i). Fig. 13h shows the 3D model of the beam and hex- (FeS) nanotubes using sulfurization of hematite nanowires, Nano Lett. 6 (2013)
agonal wires. 2423–2430.
[15] J.M. Lucas, C.C. Tuan, S.D. Lounis, D.K. Britt, R. Qiao, W.L. Yang, A. Lanzara, A.P.
Alivisatos, Ligand-controlled colloidal synthesis and electronic structure
characterization of cubic iron pyrite (FeS2) nanocrystals, Chem. Mater. 25
4. Conclusions (2013) 1615–1620.
[16] R.A. Berner, Tetragonal iron sulfide, Science 137 (1962) 669.
In summary, various corrosion products via the reaction of iron [17] A.G. Wikjord, T.E. Rummery, F.E. Doern, D.G. Owen, Corrosion and deposition
during the exposure of carbon steel to hydrogen sulphide–water solutions,
and hydrogen sulfide in both vapor and liquid phases are identi- Corros. Sci. 20 (1980) 651–671.
fied. The initial product is determined as an Fe–S nanocrystal, [18] D.W. Shoesmith, P. Taylor, M.G. Bailey, D.G. Owen, The formation of ferrous
and troilite is the final main phase in the H2S–H2O vapor environ- monosulfide polymorphs during the corrosion of iron by aqueous hydrogen
sulfide at 21 °C, J. Electrochem. Soc. 127 (1980) 1007–1015.
ment. The sequence of the main products is mackinawite + cubic [19] J. Kvarekval, R. Nyborg, H. Choi, Formation of multilayer iron sulfide films
FeS ? troilite through the immersion of steel in oxygen-free solu- during high temperature CO2/H2S corrosion of carbon steel, NACE
tions saturated with H2S at 50 °C and 1 MPa pressure. Mackinawite International, 2003, Paper No. 03339.
[20] S.N. Smith, B.N. Brown, W.N. Sun, Corrosion at higher H2S concentrations and
is the only product formed in the aqueous H2S brine solution under
moderate temperatures, NACE Corrosion/2011 Paper No. 11081, Houston,
atmospheric pressure for 168 h at different temperatures. This Texas, USA, 13–17 March, 2011.
phenomenon may have been caused by the existence of chloridion. [21] C.S. Zhou, S.Q. Zheng, C.F. Chen, G.W. Lu, The effect of the partial pressure of
H2S on the permeation of hydrogen in low carbon pipeline steel, Corros. Sci. 67
The corresponding crystal structure and micro-morphology of
(2013) 184–192.
the corrosion products are provided. Mackinawite appears with a [22] M.A. Lucio-Garcia, J.G. Gonzalez-Rodriguez, M. Casales, L. Martinez, J.G.
flake-like shape, cubic FeS has a perfect/truncated octahedral Chacon-Nava, M.A. Neri-Flores, A. Martinez-Villafañe, Effect of heat
shape, and pyrite is framboid-shaped. Troilite appears as beam or treatment on H2S corrosion of a micro-alloyed C–Mn steel, Corros. Sci. 51
(2009) 2380–2386.
hexagonal wires during the early reaction period, and then devel- [23] S.Q. Zheng, Y.M. Qi, C.F. Chen, S.Y. Li, Effect of hydrogen and inclusions on the
ops into flower-like structures. Flower-like troilite develops from tensile properties and fracture behaviour of A350LF2 steels after exposure to
beam- or hexagonal wire-shaped grains through electrostatic wet H2S environments, Corros. Sci. 60 (2012) 59–68.
[24] J.B. Sardisco, W.B. Wright, E.C. Greco, Corrosion of iron in on H2S–CO2–H2O
interactions along a certain lattice plane. The large single beam- system: corrosion film properties on pure iron, Corrosion 21 (1965) 450.
shaped troilite has a growth pattern along the c axis and planar [25] T.A. Ramanarayanan, S.N. Smith, Corrosion of iron in gaseous environments
defects that are predominantly stacking faults, which are particu- and in gas-saturated aqueous environments, Corrosion 46 (1990) 66–74.
[26] E.T. Turkdogan, Fe–S system: Part I. Growth rate of FeS on Fe and diffusivities
larly perpendicular to the c axis. Finally, 3D models for these of Fe in FeS, Trans. AIME 242 (1968) 1665–1672.
corrosion products are generated. [27] A. Dravnieks, C.H. Ssmans, Kinetics of reaction of steel with hydrogen sulfide–
hydrogen mixtures, J. Electrochem. Soc. 105 (1958) 183–191.
[28] H.P. Wang, I. Salveson, A review on the mineral chemistry of the non-
Acknowledgements stoichiometric iron sulphide, Fe1vS (0 6 v 6 0.125) polymorphs: phase
relations and transitions, electronic and magnetic structures, Phase Transit.
78 (2005) 547–567.
This work was financially supported by the Natural Science [29] Q.Y. Liu, L.J. Mao, S.W. Zhou, Effects of chloride content on CO2 corrosion of
Foundation of China (Nos. 51171208 and 51271201) and the carbon steel in simulated oil and gas well environments, Corros. Sci. 60 (2014)
Science Foundation of China University of Petroleum, Beijing, China 165–171.
[30] Y.M. Qi, H.Y. Luo, S.Q. Zheng, C.F. Chen, Z.G. Lv, M.X. Xiong, Effect of
(No. LLYJ-2011-41). temperature on the corrosion behavior of carbon steel in hydrogen sulphide
environments, Int. J. Electrochem. Sci. 9 (2014) 2101–2112.
[31] J.B. Sardisco, R.E. Pitts, Corrosion of iron in an H2S–CO2–H2O system
References composition and protectiveness of the sulfide film as a function of pH,
Corrosion 21 (1965) 350–354.
[1] R.D. Kane, M.S. Cayard, NACE Committee Report 8X294: Review of Published [32] Y.M. Qi, H.Y. Luo, S.Q. Zheng, C.F. Chen, D.N. Wang, Effect of immersion time on
Literature on Wet H2S Cracking, NACE Corrosion/99, San Antonio, TX, 1999. the hydrogen content and tensile properties of A350LF2 steel exposed to
[2] W. Lee, Z. Lewandowski, P.H. Nielsen, W.A. Hamilton, Role of sulfate-reducing hydrogen sulphide environments, Corros. Sci. 69 (2013) 164–174.
bacteria in corrosion of mild steel: a review, Biofouling 8 (1995) 165–194. [33] D.S. Li, M.H. Nielsen, J.R.I. Lee, C. Frandsen, J.F. Banfield, J.J. De Yoreo, Direction-
[3] S.Q. Zheng, C.Y. Li, Y.M. Qi, L.Q. Chen, C.F. Chen, Mechanism of (Mg, Al, Ca)- specific interactions control crystal growth by oriented attachment, Science
oxide inclusion-induced pitting corrosion in 316L stainless steel exposed to 336 (2012) 1014–1018.
sulphur environments containing chloride ion, Corros. Sci. 67 (2013) 20–31. [34] A.C. Scheinost, L. Charlet, Selenite reduction by mackinawite, magnetite and
[4] D. Rickard, J.W. Morse, Acid volatile sulfide (AVS), Mar. Chem. 97 (2005) siderite: XAS characterization of nanosized redox products, Environ. Sci.
141–197. Technol. 42 (2008) 1984–1989.
[5] L. Zhang, P. De Schryver, B. De Gusseme, W. De Muynck, N. Boon, W. Verstraete, [35] M. Wolthers, S. Gaast, D. Rickard, The structure of disordered mackinawite,
Chemical and biological technologies for hydrogen sulfide emission control in Am. Mineral. 88 (2003) 2007–2015.
sewer systems: a review, Water. Res. 42 (2008) 1–12. [36] A.R. Lennie, S.A.T. Redfern, P.F. Schofield, D.J. Vaughan, Synthesis and Rietveld
[6] R. Cabrera-Sierra, E. Sosa, M.A. Pech-Canul, I. González, The impedance crystal structure refinement of mackinawite, tetragonal FeS, Mineral. Mag. 59
characteristics of protective corrosion films on carbon steel in an alkaline (1995) 677–684.
sour medium, Electrochim. Acta 51 (2006) 1534–1540. [37] A.R. Lennie, S.A.T. Redfern, P.E. Champness, C.P. Stoddart, P.F. Schofield, D.J.
[7] M. Alizadeh, S. Bordbar, The influence of microstructure on the protective Vaughan, Transformation of mackinawite to greigite: an in situ X-ray powder
properties of the corrosion product layer generated on the welded API X70 diffraction and transmission electron microscope study, Am. Mineral. 82
steel in chloride solution, Corros. Sci. 70 (2013) 170–179. (1997) 302–309.
[8] R.J. Jiang, C.F. Chen, S.Q. Zheng, The non-linear fitting method to analyze the [38] A. Devey, N.H. De Leeuw, Density functional theory study of the high-and
measured M–S plots of bipolar passive films, Electrochim. Acta 55 (2010) low-temperature phases of cubic iron sulfide, Phys. Rev. B 82 (2010)
2498–2504. 235112.
[9] H.Y. Ma, X.L. Cheng, G.Q. Li, S.H. Chen, Z.L. Quan, S.Y. Zhao, L. Niu, The influence [39] M. Pósfai, P.R. Buseck, D.A. Bazylinski, R.B. Frankel, Reaction sequence of iron
of hydrogen sulfide on corrosion of iron under different conditions, Corros. Sci. sulfide minerals in bacteria and their use as biomarkers, Science 280 (1998)
42 (2000) 1669–1683. 880–883.
406 P. Bai et al. / Corrosion Science 87 (2014) 397–406

[40] S. Takeno, H. Zoka, T. Niihara, Metastable cubic iron sulfide-with special [47] J.B. Murowchick, H.L. Barnes, Marcasite precipitation from hydrothermal
reference to mackinawite, Am. Mineral. 55 (1970) 1639–1649. solutions, Geochim. Cosmochim. Acta 50 (1986) 2615–2629.
[41] E. Bertaut, Structure de FeS stoichiometrique, Bull. Soc. Franc. Mineral. Cristall. [48] C. Wadia, Y. Wu, S. Gul, S.K. Volkman, J.H. Gou, A.P. Alivisatos, Surfactant-
79 (1956) 276–292. assisted hydrothermal synthesis of single phase pyrite FeS2 nanocrystals,
[42] H.T. Evans, Lunar troilite: crystallography, Science 167 (1970) 621–623. Chem. Mater. 21 (2009) 2568–2570.
[43] H.E. King, C.T. Prewitt, High-pressure and high-temperature polymorphism of [49] R.E. Sweeney, I.R. Kaplan, Pyrite framboid formation; laboratory synthesis and
iron sulfide (FeS), Acta Crystallogr. B 38 (1982) 1877–1887. marine sediments, Econ. Geol. 68 (1973) 618–634.
[44] R.A. Berner, Thermodynamic stability of sedimentary iron sulfides, Am. J. Sci. [50] D.W. Shoesmith, T.E. Rummery, M.G. Bailey, D.G. Owen, Electrocrystallization
265 (1967) 773–785. of pyrite and marcasite on stainless steel surfaces, J. Electrochem. Soc. 126
[45] P.H. Tewari, A.B. Campbell, Dissolution of iron during the initial corrosion of (1979) 911–919.
carbon steel in aqueous H2S solutions, Can. J. Chem. 57 (1979) 188–196.
[46] R. de Medicis, Cubic FeS, a metastable iron sulfide, Science 170 (1970) 1191–
1192.

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