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Oxid Met

DOI 10.1007/s11085-015-9567-y

ORIGINAL PAPER

Effects of Sulfides on the Corrosion Behavior of Inconel


600 and Incoloy 825 in Supercritical Water

Yanhui Li1 • Shuzhong Wang1 • Xingying Tang1 •

Donghai Xu1 • Yang Guo1 • Jie Zhang2 •


Lili Qian1

Received: 17 May 2015 / Revised: 17 June 2015


Ó Springer Science+Business Media New York 2015

Abstract Corrosion tests of Inconel 600 and Incoloy 825 were performed in
supercritical water containing sulfides at 520 °C and 25 MPa. The scales formed on
Inconel 600 consisted of a thick outer layer of almost pure Ni3S2 and an inner layer
predominantly of Cr-rich spinels with a Ni3S2 network inside. The scales of Incoloy
825 also had a multilayered structure. The outer layer primarily consisted of Ni3S2
and (Ni,Fe)3S4, followed by a thicker intermediate mixture layer of chromium-rich
oxides, Ni3S2, and (Ni,Fe)3S4, an inner layer of predominantly Cr2O3 and a small
amount of Ni3S2 toward the substrate. Incoloy 825 showed slightly better corrosion
resistance than Inconel 600 due to its higher Cr content. By means of superimposed
isothermal phase diagrams and evaluation for the partial pressures of oxygen and
sulfur in the designated atmosphere, the corresponding corrosion mechanisms were
discussed, based on the present investigation.

Keywords Inconel 600  Incoloy 825  Supercritical water  Sulfides  Corrosion


mechanism

Introduction

A large amount of organic wastewater containing sulfides has been produced from
Industrial production. In addition to large numbers of organic pollutants, it also
contains some inorganic sulfur-containing species, predominantly of S2-, HS-1 and/
or H2S, causing diverse impacts on human health and natural ecological environment.

& Shuzhong Wang


szwang@aliyun.com
1
Key Laboratory of Thermo-Fluid Science and Engineering of MOE, School of Energy and
Power Engineering, Xi’an Jiaotong University, Xi’an 710049, Shaanxi, China
2
State Key Laboratory Base of Eco-hydraulic Engineering in Arid Area, Xi’an University of
Technology, Xi’an 710048, Shaanxi, China

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By capitalizing on the properties of water in the supercritical region (above 374.15 °C


and 22.1 MPa for pure water), supercritical water oxidation (SCWO) proposed by
Modell at the Massachusetts Institute of Technology in the early 1980s, has been
proven to be an efficient and clean technology to treat a variety of organic wastes [1].
Due to the absence of mass transfer resistance between organic compounds and
oxidants (such as oxygen and peroxide) that are mutually soluble, the spontaneous and
rapid oxidation of almost any pollutant is obtained with a very high destruction and
removal efficiency (DRE) not less than 99 % at typical operation conditions of
25 MPa, 550 °C, and residence times of 60 s or less. During the SCWO process, the
organic compounds are oxidized completely by oxidants into CO2 and H2O. Organic
nitrogen is predominately converted into N2 with/without small amounts of N2O. The
hetero-atoms chlorine, sulfur, or phosphorus present in the organic wastes, are
transformed into corresponding mineral acids of HCl, H2SO4, or H3PO4, respectively.
In particular, the sulfides in aqueous wastes can be ultimately oxidized into sulfate [2].
Up to now, the research for more than three decades has resulted in a significant
maturation of SCWO technology, and full-scale application has become the focus of
SCWO technology. It has been proved that SCWO systems have the potential to
address a variety of high concentration refractory and/or toxic organic wastewaters,
such as sulfide-containing wastewater and municipal sludge, in an environment-
friendly, efficient and economical way.
The SCWO is a high temperature and pressure oxidizing reaction, generally the
feeds need to be preheated up to supercritical conditions. Thus, it is of great
significance to understand the corrosion behavior of candidate materials under
supercritical water environments without additional oxidants, corresponding to the
preheating stage of SCWO. With higher mechanical strength and better corrosion
resistance compared to carbon steel or stainless steel at high temperatures [3–8], Ni-
based alloys are generally considered as the candidate materials for fabricating
supercritical water reactors and other pipes & equipment working under supercrit-
ical condition. At present, many nickel-based alloys such as Alloy 625, Inconel 600,
Alloy 690, Alloy 718 and Alloy C-276, have been investigated as candidate
materials in pure supercritical water (SCW) [8–11]. The oxide films formed on
nickel-based alloy surface exposed to pure SCW generally show a duplex layer
structure with Ni and Fe rich in the outer layer, and Cr rich in the inner layer, which
effectively hinder the outward diffusion of alloying elements and the inward
diffusion of oxygen ions, thus reducing corrosion rate of the substrate. Differing
from the working fluids employed in supercritical power plants and conceptual
supercritical water cooled reactors (as one of the generation IV nuclear reactor), the
feed streams present in supercritical heater for supercritical water oxidation and
gasification usually also contain large quantities of organic compounds and
inorganic salts. Aggressive inorganic anions derived from the inorganic salts, such
as Cl–, Br-, NO3-, SO42-, and PO42-, can promote or inhibit the rates of different
corrosion processes under supercritical water environments, depending on how they
interact with the protective oxide layers. The localized corrosion (e.g. pitting
corrosion and stress corrosion cracking) is commonly known for chloride, and
bromide [12–14]. However, Several anions, such as phosphate [15], can be

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incorporated in the oxide layer of nickel-based alloys and lead to their increased
stability because of secondary passivation.
However, there has been little study on resistance of nickel-based alloys in SCW
containing sulfides. Inconel 600 and Incoloy 825 are typical Ni–Cr alloys. Despite
of less competitive edge on corrosion resistance relative to Ni–Cr–Mo alloys, such
as alloys 625 and 276, the corrosion characteristics of Inconel 600 and Incoloy 825
in SCW with/without pollutants have attracted widespread attention due to their
relatively significant economic advantages [16–18]. Hence the study on corrosion
behavior of Inconel 600 and Incoloy 825 in SCW containing sulfides would provide
a fundamental understanding of the effects of sulfides on the corrosion behavior of
nickel-based alloys in SCW. Furthermore, the study is significant to guide the pipes
& facilities material selection for industrialization implementation for the SCW
treatment of sulfide-containing wastewater and the syngas production of high-
sulfur-containing coal by supercritical water gasification. In this paper, the effects of
sulfides on the corrosion process, scale morphology, and surface microstructure of
Inconel 600 and Incoloy 825 are discussed. Further, an explanation is given to the
corrosion mechanism of Inconel 600 and Incoloy 825 in SCW containing sulfides.
On the other hand, the reactivity of the two alloys will be compared.

Experimental Procedures

The aqueous solution of pH 8.5 used for the corrosion experiments contained
12,800 ppm sulfide (precisely, bivalent sulfur content), and chemical oxygen
demand (COD) of 4800 ppm for the presence of organic compounds in real
wastewater. This aqueous solution simulated real wastewater derived industries
which generate sulfur-containing organics. The chemical compositions of Inconel
600 and Incoloy 825 used in the present work are listed in Table 1. The samples had
dimensions of about 9 9 9 9 6 mm and 8 9 8 9 10 mm for alloy Inconel 600 and
alloy Incoloy 825, respectively. A 3 mm diameter hole was drilled near the edge of
a given sample so that it could be suspended in the autoclave by an iron wire with
1 mm diameter. Samples were polished to a 1600-grit finish, cleaned in acetone and
then wrapped by absorbent paper and stored inside a silica gel drier. In order to
avoid galvanic corrosion effect, a delicate corrosion specimen holder was used,
shown in Fig. 1. As shown in the figure, the wires used to hang the test specimens
were wrapped piecewise by quartz tubes with an inner- and outer diameter of 1.5
and 2 mm respectively. An insulating ceramic chip existed between the specimens.

Table 1 Chemical composition of Inconel 600 and Incoloy 825


Alloy Ni Cr Fe Mo Ti Al Cu Others

Inconel 600 Bal. 15.51 8.26 – 0.29 0.28 0.64 0.24Si, 0.29Mn
Incoloy 825 Bal. 22.05 31.15 3.38 0.96 0.12 2.03 0.23Si, 0.67Co

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Fig. 1 Schematic diagram of a specimen holder

The experimental system used in this work consisted of a high temperature


autoclave, a temperature controller, a manual metering pump and some other
auxiliary facilities. While most parts of the used system were made of 316 stainless
steel, Hastelloy C-276 was used to make autoclave. The autoclave was designed for
a maximum pressure and temperature of 35 MPa and 650 °C, with an electrical
heating power of 3.0 kW. Other detailed information can be obtained in our
previous studies [19].
According to the expected temperature and pressure (520 °C, and 25 MPa in this
study) in the autoclave, a predetermined volume of the sulfide-containing aqueous
solution was loaded in the autoclave. After hanging the samples of Inconel 600 and
Incoloy 825 in the autoclave, the test system was sealed and then purged with
nitrogen gas for about 30 min to remove the residual air prior to heating. The
temperature can be controlled with a precision of 0.1 °C. After immerging the
samples in the autoclave at the predetermined condition for 1, 2, 3, 15, 30, 45, and
60 h, the electric heating device was shut off, and the autoclave was cooled slowly
to ambient temperature through natural ventilation to prevent the corrosion scales
produced on specimen surface from cracking and desquamating due to fast cooling.
After the experiments, the samples were transferred into the acetone solution and
deionized water to clean up, and then dried by a blower for the follow-up analysis.
After thermal exposure, the samples were visually inspected and weighted. An
Acculab balance (Satorius) with a resolution of 0.01 mg was used for weight
measurement. The samples surface were then examined using scanning electron
microscopy (SEM) equipped with energy dispersive spectroscopy (EDS) and X-ray
diffraction (XRD). After surface analysis, the sample were mounted with epoxy and
then polished to 2000-grit finish for across sectional analysis.
A JSM-6390 SEM equipped with an EDS was used to analyze the material
composition and its elements distribution. Except EDS, an electron-probe micro

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analyzer (EMPA) was also used to measure the compositional profile in the scales
and substrate of alloy Incoloy 825, because the EMPA technique provides better
analytical discrimination between molybdenum contained in alloy substrate and
sulfur derived from ambient solutions. X-ray diffraction (XRD) analysis using an
X’PertProMPD Diffractometer was conducted to determine the phases in the
samples after exposure tests. The scanning range was controlled within
2h = 20–908 with a step size of 0.001°. Cu ja radiation generated at 60 kV and
55 mA was used for diffraction. The X’pert Graphics and Identify programme was
used to identify particular phases using the Joint Committee on Power Diffraction
(JCPDF) database. A sequential abrading/XRD analysis technique was adopted to
determine the spatial distribution of different phases within the scale.

Results

The Effect of Exposure Times on Corrosion Behavior

The corrosion behavior of the Inconel 600 and Incoloy 825 was investigated in
SCW with a sulfide content of 12,800 ppm at 520 °C and a pressure of 25 MPa. The
change of weight gain versus duration of exposure time from 1 to 3 h and parabolic
plots of the corrosion kinetics with an exposure time of 3–60 h are shown in Fig. 2.
As shown in the figure, the weight gain of Incoloy 825 was less than that of Inconel
600. Clearly, the corrosion resistance of Incoloy 825 was slightly better than that of
Inconel 600. For two alloys, over a certain period between 2 and 3 h, the change of
weight gain changed from a low rate to a high rate, which suggested the occurrence
of breakaway corrosion, i.e., accelerated weight-gain kinetics. The fitting curves
with an exposure time from 3 to 60 h, show a linear relationship between the

Fig. 2 Corrosion kinetics and fitting curves (from 3 to 60 h) for Inconel 600 and Incoloy 825 tested in
SCW with sulfides at 520 °C

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squared values of weight gain per unit area, denoted as DW2 and exposure time,
with the correlation coefficients of up to 0.99 and 0.96 for Inconel 600 and Incoloy
825, respectively. Thus, the function relationship from 3 to 60 h can be noted as
DW2 = k  t ? b, where t represents variable exposure time in h, while k is the
corrosion constant that approximately equates to 1.07 9 10-4 and 8.07 9 10-5 g2
cm-4 h-1 for Inconel 600 and Incoloy 825, respectively. For two alloys, the weight
change followed a parabolic law, indicating that the corrosion rate from 3 to 60 h
was controlled by a diffusion process [20–22].

Surface Morphology

Figure 3 shows the surface morphology of scales on Inconel 600 and Incoloy 825
specimens after 3 and 60 h exposure. After 3 h test, thin scales might have been
produced on samples surface of Inconel 600 and Incoloy 825. The former probably
owned thicker scales than that of Inconel 825 with minor scratches left by abrasive
paper still visible, seen in Fig. 3a, b. All corrosion products present on sample
surface layer of two alloys approximately showed a dual phase type with dark and
bright contrast. EDS analysis indicated that the dark and bright phases (marked in
Fig. 3a, b, respectively) were likely to be sulfides and oxides, respectively.
Futhermore, it may be noted that the dark phases appearing on the Inconel 600

Fig. 3 SEM images of the surface morphology of Inconel 600 and Incoloy 825 specimens after exposure
to SCW with sulfide of 12,800 ppm at 520 °C for 3 and 60 h a Inconel 600 for 3 h, b Incoloy 825 for 3 h,
c Inconel 600 for 60 h, d Incoloy 825 for 60 h

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specimen, the particle size of which was relatively less than that of bright phases,
evenly covered almost the whole surface, while a portion of the Incoloy 825 surface
was not occupied by the dark sulfide phases. The fast outward diffusion of cations
coupled with a high sulfur potential in present atmosphere led to formation of
sulfides with fast growth rates, so they occupied a large portion of the scale surface.
After exposing for 60 h, it was found that the surface of both alloys was covered by
a thick layer of corrosion products with a color of metallic light bronze. Compared
to Inconel 600, the surface color of Incoloy 825 was more somber. In addition, the
corrosion products on Inconel 600 was brittle and easy to be peeled off from the
substrate under slight tapping, while the scales formed on Incoloy 825 showed good
adhesion to the matrix. The surface morphology after exposure of 60 h are shown in
Fig. 3b, c. The surface scales of Inconel 600 and Incoloy 825 had a composition of
71.1Ni-1.7O-28.9S and 4.8Cr-69.6Ni-1.3Fe-6.5O-17.8S in wt% respectively, as
seen in Fig. 4.

Cross-Sectional Analysis

Figure 5 shows the cross sectional BSE image with EDS mapping of Inconel 600
after testing for 60 h. It can be seen from Fig. 5a that the scales on alloy Inconel 600
consisted of an inner and an outer layer indicated as A, B in the image. The interface
between two zones was approximately straight, which may be the initial alloy
surface. The thicknesses of the inner and outer layers of Inconel 600 scale were
about 80.2 and 121.9 lm, respectively. The composition of layers A, B, and C can
be found in Fig. 4. As seen in the figure, the inner layer A had a composition of
33.6Cr-11.2Ni-16.8Fe-35.9O-2.5S (in wt%) suggesting it mainly consisted of
chromium-rich oxides and a small amount of sulfides. The outer layer B
predominantly consisted of nickel sulfide with a composition of 69.8Ni-1.8O-

Fig. 4 Elements distribution on several specified areas of Inconel 600 and Incoloy 825 exposed to SCW
containing sulfides

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Fig. 5 Backscatter electron image along with EDS element intensity maps for Cr, Ni, Fe, O, and S from
the cross-section of Inconel 600 sample exposed to SCW (520 °C,25 MPa) containing 12,800 ppm
sulfide for 60 h

28.4S (in wt%). Layer C is epoxy resin layer with a carbon content up to 97.5 wt%.
The results of EDS element mapping correspond to the composition of each layer.
XRD analysis was conducted on the surface scales of Inconel 600 at different
scale depths, as seen in Fig. 6. The Ni3S2 layer was detached upon slight hitting, and
the remaining inner layer was analyzed again. The inner layer consisted primarily of
spinel-type phase, with a small amount of Ni3S2. Since XRD patterns for spinels
containing Fe, Cr, and Ni are very similar, the spinel type couldn’t be identified by
XRD analysis. However, according to the composition of inner layer A 33.6Cr-
11.2Ni-16.8Fe-35.9O-2.5S (wt%), the spinel phase FeCr2O4 might exist with a very
small amount of Ni sulfide. The main corrosion products in the inner layer were
significantly different from those of the inner subscale appearing on the Inconel 600
exposed to pure SCW. For the latter, the inner layer was generally composed of
NiCr2O4 phase. In the present work, the absence of the NiCr2O4 phase in the inner
layer might result from lower oxygen partial pressure here than that in pure SCW.
For alloy Inconel 600, the presence of planar interface between alloy substrate and

Fig. 6 XRD patterns of scales formed on alloy Inconel 600 exposed to SCW with sulfides for 60 h

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scale suggested that either the outward diffusion of Ni or inward diffusion of sulfur
is rate controlling.
The cross-sectional BSE image and EPMA line-scan profiles of the corrosion
products formed on alloy Incoloy 825 after exposure for 60 h are shown in Fig. 7.
The scales formed on alloy Incoloy 825 were also multilayered, consisting of a Cr-
rich oxide inner layer and a Ni-rich outer layer. XRD analysis was also conducted at
different scale depths of alloy Incoloy 825. As seen in Fig. 8, the top scale consisted
of Ni3S2 and a small amount of (Ni,Fe)3S4 and Cr2O3. This corresponds to alloy
surface composition of 4.8Cr-69.4Ni-13Fe-6.5O-17.8S. The presence of Ni3S2,
(Ni,Fe)3S4, Cr2O3, and spinel-type phase were all detected in the intermediate and
inner layers, except that CrS was only detected in the inner layer. However, the
Cr2O3 was more dominant in the inner layer compared to that in the intermediate
layer. Figure 9 shows the high magnification images of alloy Inconel 600 and
Incoloy 825 after testing for 60 h. As seen in the figure, for alloy Incoloy 825, the

Fig. 7 Cross-sectional a back-scattering electron image and b EPMA line-scan profiles of the corrosion
layer on alloy Incoloy 825 after the exposure for 60 h in SCW (520 °C, 25 MPa) with 12,800 ppm sulfide

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Fig. 8 XRD patterns of scales formed on alloy Incoloy 825 exposed to SCW with sulfides at different
scale depths for 60 h

Fig. 9 Corrosion layer structures representing well maintained scales formed on a Inconel 600 and
b Incoloy 825 under higher magnification

thickness of each layer toward the substrate was measured to be 25.1, 70.2 and
28.4 lm, respectively.

Discussion

For above-mentioned Inconel 600 and Incoloy 825, the scales obtained in sulfide-
containing SCW presented significant difference with those formed on general
nickel-based alloys tested in SCW with/without oxygen [7, 9, 23–27]. The latter
scales generally showed a duplex oxide structure with Ni and Fe rich in the outer
layer, and Cr rich in the inner layer. The discrepancy between the scales gained in
the present work and those in the previous studies could be attributed to the

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existence of sulfur-bearing species in SCW environment, which derived from


sulfides present in initial aqueous solutions.
Assuming that the present form of sulfides was Na2S and the partial pressure of
steam was approximative 25 MPa, the calculation of standard free energy change
for Eq. 1 at 520 °C was carried out.
Na2 S þ 2H2 O ¼ H2 S(g) þ NaOH DG0 ¼ 9:8 kJ ð1Þ

The negative standard free energy change of -9.8 kJ suggested that in SCW
environment H2S molecule was more likely to be the common form of bivalent
sulfur originally present in ambient wastewater. So it can be concluded that the
exposure environment in this study could be regarded as H2S-SCW atmosphere with
higher partial pressure of steam. Among these gases, H2S can react with metal to
form sulfides. With the defect structures and transport properties theory, it is
deduced that the growth mechanisms of most metal sulfides and oxides are
analogous, because they exhibit similar predominant defects. However, the sulfides
of common metals, such as iron, nickel, and chromium, generally have higher defect
concentration due to their much larger deviations from stoichiometry than
individual corresponding oxides [22, 28, 29], so that in present SCW environment
containing H2S, the Inconel 600 and Incoloy 825 showed poor corrosion resistance.
The superimposed isothermal phase diagram of the ternary Ni–O–S, Cr–O–S,
and Fe–O–S systems with an indication of partial pressure of oxygen (PO2) and
sulfur (PS2), calculated at 520 °C and 0.1 MPa using appropriate thermodynamic
data [30], is shown in Fig. 10. The current corrosion tests were carried out at a

Fig. 10 Isothermal cross section of the simplified Ni–Cr–Fe–O–S phase at 520 °C, formed by
superimposition for the Ni–O–S (solid line), Cr–O–S (dash line), and Fe–O–S (dot line) phase diagrams

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pressure of 25 MPa, but the phase diagram was built at 0.1 MPa because of the
absence of thermodynamic data at higher pressure. While the high pressure is
expected to make difference on the fugacity of oxygen (fO2) and sulfur (fS2), the
fugacity coefficients of oxygen (uO2) is less than 1.2 at approximative present
condition (500 °C and 25 MPa) [31]. Based on the above data, Tan et al. [32]
reported that the difference between the phase diagrams before and after correction
by the fugacity of oxygen (f O2 ¼ uO2 pO2 ) at 500 °C and 25 MPa was found to be
negligible. Along with the consideration of the similarity between the fugacity
coefficients of oxygen (uO2) and sulfur (uS2), therefore, the isothermal phase
diagrams calculated at 0.1 MPa is a reasonable estimation of the expected behavior
at higher pressure. The diagram was schematic in that all the oxide phase and the
sulfide phase for nickel, chromium, and iron had not been included. Even though the
alloys (the activity of both Ni, Cr, and Fe, etc. is less than unity) were exposed to the
mixed gas during corrosion, the above phases diagram can also be used to a first
approximation to predict the phase stability. Base on the assumption that the C/H
atomic ratio of organic compounds present in current feed was equal to
approximately 1/4 and hydrogen yield (the ratio of hydrogen moles present in
hydrogen divided by that inherent in original organic compounds) was 1.2 [33],
partial pressure of hydrogen was estimated. Then, the partial pressure of oxygen and
sulfur for the present gas composition were estimated to be *1 9 10-23 and
*2 9 10-7 atm. based on the decomposition equilibrium of H2O [34] and H2S at
520 °C, respectively, which marked as a pentagram was depicted in Fig. 10.
Also for the Ni–Cr–Fe–O–S system, the mixed gas composition was located in
the Ni3S2 and Cr2O3 stability region. In addition, the partial pressure of oxygen was
always lower than the dissociation pressure of both NiO and Fe2O3. Thus, there is
no kinetics mechanism which may allow the formation of NiO and Fe2O3 during the
corrosion of Inconel 600 and Incoloy 825 in the present mixed species. These
phenomena were in agreement with the XRD analysis results (Figs. 6, 8) and the
scale structures shown in the Fig. 9.
Since partial pressure of sulfur in the atmosphere was also much higher than CrS
dissociation pressure, once the Inconel 600 came in contact with H2S and H2O at
520 °C, the simultaneous nucleation of chromium sulfide, Cr2O3 and Ni3S2 [20, 35]
would happen at the alloy/gas interface, respectively, with the following reactions:
Cr þ H2 S ¼ CrS þ H2 ð2Þ

2Cr + 3H2 O ¼ Cr2 O3 + 3H2 ð3Þ

3Ni þ 2H2 S ¼ Ni3 S2 þ 2H2 ð4Þ

However, due to the less thermodynamic instability of CrS phase than that of
Cr2O3 phase in present gas composition, the former may react with oxygen to
further convert into Cr2O3 phase as the chromium activity decreased. Labranche
et al. indicated that early stages of corrosion in H2–H2O–H2S gas mixtures can be
explained by competitive adsorption of H2O and H2S molecules, by assuming that
the relative amount of sulfide formed initially depends on the relative rates of

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adsorption of H2O and H2S on alloys surface [35]. Although some sulfide formed on
initial exposure, protective Cr-rich oxide scales quickly formed on alloy Inconel 600
surface because supply rate of oxygen (H2O) was much greater than that of sulfur
(H2S) with molar ratio of H2O/H2S & 78. The formed Cr2O3 scales inhibited the
outward diffusion of cations and inward ingress of aggressive species, such as H2O
and H2S, during the exposure time from 1 to 2 h. It is well known that the partial
pressure of oxygen needed for a continuous Cr2O3 layer to develop on an alloy
surface was usually at least 102–105 times higher than the Cr2O3–CrS/Cr2S3
equilibrium value [36]. The formation of the continuous chromium-rich oxides layer
was supported by the above standpoint, because the present gas composition was
quite far from the Cr3S2–Cr2O3 equilibrium line with the partial pressure of oxygen
about 106 times higher than the equilibrium value (see Fig. 10). After a certain
initial stage of relatively low weight gains, alloy Inconel 600 suffered breakaway
corrosion between 2 and 3 h. This well explained why the weight gains increased
sharply from 2 to 3 h, as seen in Fig. 2. The occurrence of breakaway corrosion can
be attributed to the formation of an sulfide network in Cr2O3 scales due to ingress of
sulfur by solid-state diffusion of sulfur through oxides or by transport of H2S
through cracks or pores [23, 35–38]. The continuous formation and growth of oxides
and sulfides resulted in the formation of inner layer. Under this process, the solid-
state inward diffusion of sulfur probably predominated because of the higher
diffusion rate of sulfur relative to oxygen in Cr2O3 layer [36] and the absence of
larger cracks for H2S through inside the inner layer of alloys in this work. The
presence of the inner layer rich in chromium oxide phases in contact with the alloy
was able to reduce the corrosion rate of alloy Inconel 600 due to its barrier action to
the nickel outward diffusion. But the reduction degree was limited, because the
inner layer also contained a network of Ni3S2 phases, which provided a rapid
transport path for outward diffusion of metal ions and ingress of oxygen and sulfur
[39]. Cations from the alloy substrate, particularly nickel ions, quickly diffused
outward across the sulfide network inside the inner layer, and then encountered with
H2S moles to form sulfides at scale/gas interface [20]. During the corrosion of the
Ni-rich alloy at high temperatures, combining with the fact that Ni3S2 grew very
rapidly in view of its highly defective nature, it was reasonable to expect the rapid
generation of a thicker Ni3S2 film as the outer subscale.
For the thicker Ni3S2 subscale in alloy Inconel 600, it grew essentially by means
of the outward diffusion of nickel, because the diffusion coefficient of nickel in
Ni3S2 was several orders of magnitude bigger than that of sulfur [22, 28, 40]. The
formation of oxides and sulfides in the inner layer suggested that the ingress of
oxygen and inward diffusion of sulfur had occurred. The inward diffusion of oxygen
through the outer Ni3S2 layer could proceed by two means: oxygen ions diffusion
and oxygen-bearing molecule transport [41, 42]. Rahmel et al. pointed out that the
diffusion coefficient of oxygen ion in sulfide was rather small [40]. So the oxygen-
bearing molecules (i.e. H2O) might be the main oxygen provider for the inner layer
oxides, which were able to penetrate through the external Ni3S2 layer, probably
through discontinuities of the outer layer such as pores and cracks, specifically
observed on the scale surface as shown in the Fig. 3c. The water molecules reached
the inner surface of the external Ni3S2 generally dissociated into oxygen and

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hydrogen. The oxygen in the form of O2- diffused inward continuously and reacted
with metal to produce metal oxides, which composited to chromium-rich spinel-
type phase [7, 43–45]. The sulfur diffusing inward through the inner layer to form
sulfides, derived the dissociation of H2S molecules. The H2S molecules reached the
inner/outer layer interface by inward transport through the cracks or pores inside the
external Ni3S2 layer. The inward transport resistance of H2S was significantly larger
than that of H2O, due to the former’s larger molecular diameter. It well explained
the cause that the inner layer was predominantly of oxides whereas the external
layer mostly consisted of sulfides.
This initial corrosion stage of Incoloy 825 was similar to that of Inconel 600,
which included the formation and subsequent cracking of protective chromium-rich
oxide scales. Over the early stage of exposure, a continuous chromium-rich oxide
layer preferentially occurred at alloy Incoloy 825 surface. Some physical defects
inside the chromium-rich layer could act as the preferential location for the inward
ingress of sulfur-containing species, leading to the formation of sulfides. Eventually
a series of micro channels of sulfides were built up across the chromium-rich oxide
layer. Similar to alloy Inconel 600, as the corrosion process proceeded, the
breakaway corrosion of alloy Incoloy 825 also happened after 2–3 h of exposure.
After that, the outward diffusion of cations, such as iron, nickel, and chromium,
across the micro channels of sulfides, and subsequent formation of their sulfides on
the chromium-rich oxides layer, resulted in the formation and development of the
outer layer. It was worth mentioning that the current gas composition was located
near the FeS-Fe3O4 equilibrium line, slightly inclined to the Fe3O4 phase region.
Considering the higher iron activity on the Incoloy 825 surface, thereupon all the
formation of FeS and Fe3O4 was likely to be involved in the corrosion process. At
the same time, according to the fact that the growth kinetics of nickel sulfide is
much faster than those of other sulfides [20], a portion of Ni3S2 might react with FeS
to produce violarite [(Ni,Fe)3S4/NiFe2S4] phase via the following reaction (Eq. 5)
[46]:
Ni3 S2 þ 6FeS þ 2S2 ¼ 3NiFe2 S4 ð5Þ

4Cr2 O3 + Fe3 O4 + Fe = 4FeCr2 O4 ð6Þ

Of course, the higher oxygen affinity of chromium than that of iron and nickel
decided the preferential oxidation of chromium to produce Cr2O3. Thus, the outer
scale consisted of Ni3S2 and a small amount of (Ni,Fe)3S4 and Cr2O3. At the same
time, the inner layer gradually thickened with the continuous formation of oxides
and sulfides by the ingress of oxygen and sulfur. A part of Cr2O3 reacted with Fe3O4
to form spinel FeCr2O4 by the reaction shown in Eq. 6. Therefore, the spinel-type
phase was also detected in the inner layer. The intriguing point was that the CrS
phase was only detected in the inner layer rather than in the outer layer, in spite of
lower sulfur activity of the former than that of the later. This behavior was
consistent with the studies on the corrosion of Ni–Cr, Fe–Cr and Co–Cr alloys in
H2S–H2 atmosphere. Narita et al. [47]. pointed out that Cr-containing alloys were
easily sulfurated at a low sulfur activity compared to a high sulfur activity. Due to

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the much higher ions diffusion rate along the micro channels of sulfides than that
through the chromium-rich oxides layer, the barrier effects of the inner layer on the
outward diffusion of alloying elements and the inward diffusion of oxygen and/or
sulfur decreased significantly [48]. Some chromium and other substrate elements
diffused outward through the inner layer and reached the inner-outer layer interface,
and then were oxidized and/or sulfurated because of the inward ingress of sulfur and
oxygen through the outer layer, resulting in the formation of intermediate layer
predominantly composed of Cr2O3, spinel-type phase, and sulfides of nickel and
iron [49]. Incoloy 825 also contained small amounts of refractory metals, such as
Mo: 3.38 wt%. It was found that in refractory-metal (mainly Mo and Nb) sulfides,
the defect concentrations was much lower than that found in their oxides [50, 51].So
the refractory metals were sulfurated at a very low rate, almost similar to the
oxidation of chromium [52]. The molybdenum sulfide was not detected in Fig. 8,
however, which might result from their small quantity or that the molybdenum still
remained as uncorroded metal.
For alloy Inconel 600 and alloy Incoloy 825, all the ‘‘protective’’ corrosion
period lasted less than 3 h. However, the research conducted by Wu et al. [23]
indicated that the protective properties of initially formed Cr2O3 scales could keep
for 5–50 h depending on the alloy, which was exposed to relatively high PS2–low
PO2 atmosphere. In this work, the fact that the breakaway corrosion for two alloys
occurred early could be attributed to the lower content of chromium in alloy and
higher defect density of oxides formed in supercritical water atmosphere. For a
number of mechanisms proposed to account for the occurrence of breakaway
corrosion in atmosphere where a protective oxide is thermodynamically stable, the
relative kinetics of oxide and sulfide formation are of major importance [23, 36–38,
53]. The relativeness of kinetics was generally expressed by Kinetics Boundary
(K.B) defined as the threshold PO2 needed for continuous Cr2O3 layer to develop on
the surface of an alloy [53]. With the decrease of chromium content, the threshold
PO2 increases [23].In Wu’s research, the Ni-based alloy N06230 and Ni–Fe based
alloy N08120 with a chromium content of 22 wt% and 25 wt%, higher than that of
alloy Inconel 600 (*15 wt%) and alloy Incoloy 825 (*22 wt%), respectively,
almost suffered breakaway corrosion firstly among investigated alloys. For alloy
Inconel 600 and alloy Incoloy 825 with relatively lower chromium content,
therefore, the breakaway corrosion was more prone to happen after a shorter time. In
addition, with the same exposure temperatures and oxygen partial pressures, the
defect density of oxides formed in SCW is higher than that in steam environment
[54, 55]. The concentrated defects of ‘‘protective’’ oxides accelerated the ingress of
sulfur, further resulting in the loss of oxides’ protective immune function in
advance. After the occurrence of breakaway corrosion, the weight gain of two alloys
followed a parabolic law, which well agreed with the growth mechanism of scales in
which their thickening were mainly controlled by diffusion process. The corrosion
layer structure images of alloy Inconel 600 and alloy Incoloy 825, as seen in Fig. 9,
and the phase distribution in each layer, indicated that the inner layers all consisted
of predominantly chromium-rich oxides with some micro channels of sulfides
inside. Although the cations from the substrate can quickly diffuse outward across
the sulfide channels, the presence of the remaining, discontinuous chromium-rich

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Oxid Met

oxide layer still provides barrier effects on the outward of metal ions, and inward
ingress of oxygen and sulfur. The slightly better corrosion resistance of alloy
Incoloy 825 than alloy Inconel 600 was mostly due to the smaller percentage of
cross-section occupied by sulfides. Because Incoloy 825 contains higher Cr (22.05
wt%), compared to Inconel 600 (15.51 wt% [56]. In addition, Kai et al. [20]
reported that to some extent, the intermediate layer as a complex mixtures layer
could also hamper the transport of cations and anions. Thus, the outer layer of
Incoloy 825, developed by the cations outward diffusion, was thinner than that of
Inconel 600.

Conclusions

The corrosion of Inconel 600 and Incoloy 825 in sulfide-containing SCW (precisely,
SCW-H2S atmosphere) at 520 °C and 25 MPa was carried out. The presence of
sulfides deteriorated the corrosion resistance of Inconel 600 and Incoloy 825 in
supercritical water. The two alloys suffered breakaway corrosion after a certain
initial stage between 2 and 3 h. In this work, the fact that the breakaway corrosion
for both alloys occurred early, could be attributed to the lower content of chromium
and higher defect density of oxides formed in SCW environment. After the
occurrence of breakaway corrosion, there was better linear relationship between
squared values of weight gain per unit area (DW2) and exposure time (t), noted as
DW2 ¼ k  t þ b, for Inconel 600 and Incoloy 825. Their corresponding corrosion
constants of k were equal to 1.07 9 10-4 and 8.07 9 10-5 g2 cm-4 h-1,
respectively. The scale developed on Inconel 600 was obviously divided into inner
and outer layers, with the gap between the two layers approximately parallel to the
initial alloy surface. The outer layer of the formed scale was essentially of Ni3S2
phase, whereas the inner layer was predominantly of chromium-rich spinel-type
phases with a Ni3S2 network inside. As for Incoloy 825, the aspect of the scale
changed, that Ni3S2 phase and a small amount of (Ni,Fe)3S4 and Cr2O3 covered the
entire alloy surface. The presence of Ni3S2, (Ni,Fe)3S4, Cr2O3, and spinel-type
phase was all detected in the intermediate and inner layer, but Cr2O3 was mostly
constitution of the inner layer. An superimposed isothermal phase diagram of the
ternary Ni–O–S, Cr–O–S, and Fe–O–S systems at 520 °C was built, which showed
that the Ni3S2 and Cr2O3 was predominant stable phases in the predesigned
environment. This was well consistent with the obtained experimental results.
The reaction mechanism of corrosion behavior of Inconel 600 included the
outward diffusion of nickel through the inner layer and the inward transport of H2O
through the outer layer. Comparing with Inconel 600, the corrosion mechanism of
Incoloy 825 was more complex: all the inward transport of H2O, the inward
transport of H2S and/or diffusion of sulfur ion, and outward transport of cations (Ni,
Cr, and Fe) might be involved. For the two alloys mentioned above, due to stronger
inward permeation ability of H2O than that of H2S molecules, the inner layer was
predominantly of oxides whereas the external layer mostly consisted of sulfides.

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Oxid Met

Acknowledgments This work was financially supported by the Twelfth Five-Year Chinese National
Science and Technology Support Programme (2011BAK06B04).

References
1. H. Barner, C. Huang, T. Johnson, G. Jacobs, M. Martch and W. Killilea, Journal of Hazardous
Materials 31, 1 (1992).
2. T. Wang, B. T. Xiang, J. Liu and Z. Y. Shen, Environmental Science & Technology 37, 1955 (2003).
3. S. S. Hwang, B. H. Lee, J. G. Kim and J. Jang, Journal of Nuclear Materials 372, 177 (2008).
4. J. Yuan, X. Wu, W. Wang, S. Zhu and F. Wang, Oxidation of Metals 79, 541 (2013).
5. H. Xu, Z. L. Zhu and N. Q. Zhang, Oxidation of Metals 82, 21 (2014).
6. H. Xiao and D. Guzonas, Journal of Nuclear Materials 445, 298 (2014).
7. X. Zhong, E. Han and X. Wu, Corrosion Science 66, 369 (2013).
8. K. H. Chang, J. H. Huang, C. B. Yan, T. K. Yeh, F. R. Chen and J. J. Kai, Progress in Nuclear
Energy 57, 20 (2012).
9. X. Ren, K. Sridharan and T. R. Allen, Corrosion 63, 603 (2007).
10. E. Asselin, A. Alfantazi and S. Rogak, Corrosion Science 52, 118 (2010).
11. F. Huang, J. Wang, E. Han and W. Ke, Corrosion Science 76, 52 (2013).
12. Z. Szklarskasmialowska, D. Grimes and J. Park, Corrosion Science 27, 859 (1987).
13. L. F. Lin, G. Cragnolino, Z. Szklarskasmialowska and D. D. Macdonald, Corrosion 37, 616 (1981).
14. S. H. Son, J. H. Lee and C. H. Lee, Journal of Supercritical Fluids 44, 370 (2008).
15. P. Kritzer, N. Boukis and E. Dinjus, Materials and Corrosion-Werkstoffe Und Korrosion 49, 831
(1998).
16. D. G. Briceno, F. Blazquez and A. S. Maderuelo, Journal of Supercritical Fluids 78, 103 (2013).
17. T. Terachi, N. Totsuka, T. Yamada, T. Nakagawa, H. Deguchi, M. Horiuchi and M. Oshitani, Journal
of Nuclear Science and Technology 40, 509 (2003).
18. R. S. Dutta, Journal of Nuclear Materials 393, 343 (2009).
19. X. Tang, S. Wang, D. Xu, Y. Gong, J. Zhang and Y. Wang, Industrial & Engineering Chemistry
Research 52, 18241 (2013).
20. W. Kai, C. H. Lee, T. W. Lee and C. H. Wu, Oxidation of Metals 56, 51 (2001).
21. D. S. Williams, R. Moller and H. J. Grabke, Oxidation of Metals 16, 253 (1981).
22. J. C. Lee, M. J. Kim and D. B. Lee, Oxidation of Metals 81, 617 (2014).
23. X. D. Wu and B. Gleeson, Paper No. 2850, NACE Corrosion 2013, NACE International, Houston,
TX (2013).
24. Z. Shen, L. Wu, L. Zhang, Z. Duan and Y. Sun, Corrosion Science and Protection Technology 26,
113 (2014).
25. A. Machet, A. Galtayries, S. Zanna, L. Klein, V. Maurice, P. Jolivet, M. Foucault, P. Combrade, P.
Scott and P. Marcus, Electrochimica Acta 49, 3957 (2004).
26. L. Tan, X. Ren, K. Sridharan and T. R. Allen, Corrosion Science 50, 3056 (2008).
27. P. Xu, L. Y. Zhao, K. Sridharan and T. R. Allen, Journal of Nuclear Materials 422, 143 (2012).
28. W. Znamirowski, F. Gesmundo, S. Mrowec, M. Danielewski, K. Godlewski and F. Viani, Oxidation
of Metals 35, 175 (1991).
29. K. Przybylski, T. Narita and W. W. Smeltzer, Oxidation of Metals 38, 1 (1992).
30. A. Roine, Outokumpu HSC Chemistry Thermo-chemical Database Version 6.0 (2007).
31. B. V. Gamson and K. M. Watson, National Petroleum News (1944).
32. L. Tan, Y. Yang and T. R. Allen, Corrosion Science 48, 3123 (2006).
33. A. Kruse, The Journal of Supercritical Fluids 47, 391 (2009).
34. N. Zhang, H. Xu, B. Li, Y. Bai and D. Liu, Corrosion Science 56, 123 (2012).
35. M. Labranche, A. Garrattreed and G. J. Yurek, Journal of the Electrochemical Society 130, 2405
(1983).
36. D. J. Baxter and K. Natesan, Oxidation of Metals 31, 305 (1989).
37. S. W. Kim, K. Ohla, H. Fischmeister and E. Fromm, Oxidation of Metals 36, 395 (1991).
38. K. Ohla, S. W. Kim, H. Fischmeister and E. Fromm, Oxidation of Metals 36, 379 (1991).
39. H. Li and W. Chen, Oxidation of Metals 78, 103 (2012).
40. M. Schulte, A. Rahmel and M. Schutze, Oxidation of Metals 49, 33 (1998).

123
Oxid Met

41. D. M. Gorman, R. L. Higginson, H. Du, G. McColvin, A. T. Fry and R. C. Thomson, Oxidation of


Metals 79, 553 (2013).
42. P. Berthod, L. Aranda, S. Mathieu and M. Vilasi, Oxidation of Metals 79, 517 (2013).
43. D. Rodriguez, A. Merwin and D. Chidambaram, Journal of Nuclear Materials 452, 440 (2014).
44. K. H Chang, S. M. Chen, T. K. Yeh and J. J. Kai, Corrosion Science 81, 21 (2014).
45. H. L. Hu, Z. J. Zhou, L. Liao, L. F. Zhang, M. Wang, S. F. Li and C. C. Ge, Journal of Nuclear
Materials 437, 196 (2013).
46. F. Jorgensen and P. Koh, JOM 53, 16 (2001).
47. T. Narita and T. Ishikawa, Materials Science and Engineering 87, 51 (1987).
48. C. S. Giggins and F. S. Pettit, Oxidation of Metals 14, 363 (1980).
49. H. Li and W. Chen, Oxidation of Metals 77, 107 (2012).
50. Y. R. He, D. L. Douglass and F. Gesmundo, Oxidation of Metals 37, 413 (1992).
51. Y. R. He, D. L. Douglass and F. Gesmundo, Oxidation of Metals 37, 217 (1992).
52. H. L. Du, P. K. Datta, J. S. Gray and K. N. Strafford, Corrosion Science 36, 99 (1994).
53. H. Xu, M. G. Hocking and P. S. Sidky, Oxidation of Metals 41, 81 (1994).
54. Y. Otoguro, M. Sakakibara, T. Saito, H. Ito and Y. Inoue, Trans. Iron Steel Inst. Jpn. 28, 761 (1988).
55. S. Guillou, C. Cabet, C. Desgranges, L. Marchetti and Y. Wouters, Oxidation of Metals 76, 193
(2011).
56. M. J. Kim and D. B. Lee, Korean Journal of Metals and Materials 50, 218 (2012).

123