Corrosion Science: Pengpeng Bai, Shuqi Zheng, Hui Zhao, Yu Ding, Jian Wu, Changfeng Chen
Corrosion Science: Pengpeng Bai, Shuqi Zheng, Hui Zhao, Yu Ding, Jian Wu, Changfeng Chen
Corrosion Science: Pengpeng Bai, Shuqi Zheng, Hui Zhao, Yu Ding, Jian Wu, Changfeng Chen
Corrosion Science
journal homepage: www.elsevier.com/locate/corsci
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. 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
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.
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
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.
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