Metallogr. Microstruct. Anal.
DOI 10.1007/s13632-014-0182-0
TECHNICAL ARTICLE
Cyclic Hot Corrosion Behavior of Superni 718, Superni 600,
and Superco 605 in Sulfate and Chloride Containing Environment
at 900 °C
Deepa Mudgal • Surendra Singh • Satya Prakash
Received: 16 January 2014 / Revised: 21 November 2014 / Accepted: 22 December 2014
Ó Springer Science+Business Media New York and ASM International 2014
Abstract Superalloys are widely used for high-tempera-
ture applications. But these alloys also suffered from severe
degradation where corrosion problem frequently encoun-
tered due to the presence of molten salt deposits. To
obviate this problem, three nickel- and cobalt-based
superalloys had been exposed to (Na2SO4–25%NaCl) at
900 °C for 100 cycles. The resulting corrosion products
were characterized using scanning electron microscopy and
energy dispersive spectroscopy. It was observed that both
Ni-based alloys exhibited improved corrosion resistance
over the Co-based alloy in this aggressive environment. In
Ni-based alloys, the scale contained oxides such as NiO,
Cr2O3, Fe2O3, and spinel NiCr2O4, whereas in case of
Co-based alloy, the scale contained CoO and CoNiO2.
Keywords Superalloys  SEM  Hot corrosion
Introduction
High-temperature surfaces in waste heat boilers, inciner-
ators, and power generating equipments suffer from
chloride-induced corrosion which becomes one of the
most expensive problems in the industry. This corrosion
often necessitates replacement of superheater tubes as
often as annually in some units [1, 2]. Scroll [3] reported
that in municipal solid waste incinerator environment, the
dominant corrosive species are chlorides, typically in
combination with alkali metals (Na, K) and heavy metals
(Pb, Zn). Corrosion by chlorine (Cl2) occurs rapidly
D. Mudgal (&)  S. Singh  S. Prakash
Department of Metallurgical and Materials Engineering,
Indian Institute of Technology, Roorkee, Uttrakhand, India
e-mail: deepamudgal01@gmail.com
because most metal chlorides have low melting points and
high vapor pressures [4]. Chlorine can somehow diffuse
through oxide scales rapidly and reacts at the oxide/metal
interface with the alloying elements and forms volatile
chlorides [5]. This process is known as active oxidation
which considerably affects the performance of metallic
components in high-temperature plants such as waste
incineration, aluminum waste heat recuperation, and coal-
conversion processes [6]. It has been reported that con-
ventional steels used in superheater in the biomass fuel-
fired boilers using 100% wood fuel and with steam tem-
perature higher than 480 °C should be changed either after
four years operation or about 20,000 working hours due to
corrosion and fouling [7].
Superalloys are widely used in turbines for both aero-
space- and land-based power-generation applications, due
to their exceptional elevated-temperature strength, high
resistance to creep, oxidation, corrosion, and good fracture
toughness [8]. Oxidation property is one of the most
important aspects for any high-temperature alloy systems,
as poor oxidation resistance hinders the possible applica-
tions at elevated temperatures. Generally, it is believed that
an applicable engineering alloy should have the ability to
form an external oxide scale such as Al2O3 and Cr2O3,
sometimes SiO2 that grows at a low rate and has a damage
tolerance [9]. It was seen that the compounds of salts such
as chlorine, sodium, potassium, or vanadium along with
thermal cycles may lead to the spallation of these oxides
[10]. Oxide spallation represents a severe risk to the
maintenance of the protective oxidation conditions and
ultimately, to the endurance of the component [11]. John-
son et al. [12] reported the severe hot corrosion attack on
Ni- and Co-based alloys at 900 °C in still air with mix-
tures of NaCl/Na2SO4 containing 40 wt% NaCl. Many
researchers have studied various alloys and coatings under
123

Na2SO4–25%NaCl environment in temperature range from
650 to 900 °C [13–19]. They concluded that addition of
NaCl into Na2SO4 considerably accelerated the corrosion
of superalloys, and the corrosion scales became more
porous. Hot corrosion has been explained in terms of sul-
fide formation and subsequent oxidation [20]. Zhang et al.
[21] indicated square power law-type corrosion kinetics for
Rene 95 Ni-based alloy in a Na2SO4–25%NaCl environ-
ment. If NaCl increases to 75 percent, corrosion became
very severe as reported by Tsuar at el. [22]. CM247 alloy
was totally consumed in 90%Na2SO4-10%NaCl environ-
ment at 900 °C in 70Hr [23].
In the present study, three superalloys, i.e., alloy 718,
alloy 600, and alloy 605, have been exposed to Na2SO4–
25%NaCl environment at 900 °C for 100 cycles. Each
cycle consisted of 1 h heating in the tubular furnace at
900 °C followed by cooling in ambient air for 20 min. This
comparative study has been performed to show the sus-
tainability of these alloys under simulated environment
present in energy generating units. The environment was
chosen to simulate the corrosive conditions present in
energy generating units such as incinerators, boilers, and
gas turbines [21, 22, 24, 25]. The cyclic study has been
chosen so as to create the most aggressive environment
(more severe as compared to isothermal environment) due
to the thermal shocks. It is well known that during the time
of cooling, an alloy underwent thermal contraction,
whereas during the time of heating, the alloy undergoes
thermal expansion. This lead to the thermal expansion
mismatch between the alloy and oxide which further pro-
motes the spallation tendency of the oxide leaving the
substrate unprotective. As most of the studies reported
earlier are under isothermal condition, hence, the present
study will help examine the effect of thermal shocks on the
corrosion resistance of the alloys under molten salt envi-
ronment. The corrosion mechanisms have also been pro-
posed for all three alloys.
Experimental Details
Three superalloys, namely Superni 718, Superni 600, and
Superco 605, were procured from MIDHANI, Hyderabad,
in the form of rectangular sheets (hot rolled and annealed).
The compositions of the alloys are given in Table1. Cor-
rosion samples were cut into pieces of 20 mm 9 15 mm 9
5 mm each. All samples were mirror polished using 220,
400, 600, and 800 grit emery paper followed by alumina
polishing (1 lm). The dimensions of each sample were
measured using digital vernier caliper, and total surface
area was calculated. The hot corrosion experiments were
carried out in a silicon carbide tubular furnace at 900 °C in
still air. Alumina boats were used to keep the specimens
123
Metallogr. Microstruct. Anal.
inside the tubular furnace. Before using the boats for
experimentation, the alumina boats were heat treated at
1000 °C for 8 h. Similar heat treatment was repeated till
the weight of the boats became constant. The salt solution
was made in distilled water consisting of Na2SO4–
25%NaCl. The melting point of Na2SO4–25%NaCl is
620 °C [24]. The samples were preheated to a temperature
of 250 °C before applying the salt solution to maintain a
salt coating of about 3–5 mg/cm2. The surface area of the
samples was measured and multiplied with the amount of
salt to be coated per centimeter square. The weight of each
sample along with the boat was recorded before applying
the salt mixture. The salts were applied using camel hair
brush on the preheated specimens only once before starting
the corrosion run. The samples were then heated in the
oven at 150 °C to evaporate any water content. The sam-
ples were again weighed and checked for the amount of
coated salt. If the salt content comes out to be lower or
higher, then the desired amount of the process was again
repeated till the desired result. Before starting the cyclic
study, the weights of the salt-coated samples along with
their respective boats were noted down using digital
weighing balance having 1 mg accuracy. Similarly, the
weight was noted down after every cycle so as to know the
corrosion kinetics. Each cycle consists of 1 h heating in a
silicon carbide tubular furnace at 900 °C followed by
20 min cooling in ambient air. Similar heating and cooling
process was carried out for 100 cycles.
Results
Visual Analysis
Macrophotos of alloy 718, alloy 600, and alloy 605 after
100 cycles of exposure in molten salt environment at
900 °C are shown in Fig. 1. In the beginning of the cycles,
alloy 718 and alloy 600 both suffered with minor spallation
in the form of powder. In the case of alloy 718, the
spallation cease after 8th cycle, whereas in alloy 600, min
spalling ceases after 10th cycle. Alloy 718 when exposed in
the corrosive environment showed change in color of the
surface. The silver metallic color of specimen changes into
dark gray surface. Tint of white spots was also started
appearing from 1st cycle which intensified till 5th cycle.
After 10th cycle, no noticeable changes were recorded. In
case of alloy 600, the color of the specimen changes to dark
gray with some tint of brown color. The dark gray color
was intensified till 7th cycle. From 2nd cycle, appearance
of greenish color oxide above the dark gray oxide was also
noticed. After almost 12th cycle, no change in color or
spallation was observed. Alloy 605 experiences severe
continuous spallation in the form of flakes starting from the
Metallogr. Microstruct. Anal.

Table 1 Composition of Superalloys

Name of superalloys Elements (wt%)
Fe Ni Mn Cr Cu W Mo Co Si Ti C Nb Al

Superni600 10 max Bal. 0.5 15.5 0.3 .021

Superco605 3.0 10.0 1.5 20.0 15.0 Bal. 0.3 0.08
Superni718 18.5 Bal. 0.18 19.0 0.15 3.05 0.18 0.9 0.04 5.13 0.5

Fig. 1 Macrophotos of (a) Superni 600, (b) Superni 718, and (c) Superco 605 after cyclic hot corrosion in Na2SO4–25%NaCl at 900 °C for 100
cycles

1st cycle till almost 80th cycle. Alloy 605 developed a

lustrous silver gray oxide scale just after 1st cycle expo-
sure. Some dark gray patches were also seen on the surface.
The top oxide so formed was peeled off completely till the
end of 100rd cycles thereby reducing the thickness of the
specimens.

Thermogravimetric Studies

Weight change per unit Surface area vs Number of cycles

graph has been plotted for alloy 718, alloy 600, and alloy
605 after hot corrosion under molten salt for 100 cycles at
900 °C as shown in Fig. 2(a). Weight change noted here is
the sum of sample along with the boat. Spallad material if
any also included during the time of measurements. In case
of alloy 718 and alloy 600, maximum weight gain was
Fig. 2 Weight change/surface area vs number of cycles graph for
observed till 5th cycle after that weight change started Superni 718, Superni 600, and Superco 605 after cyclic hot corrosion
decreasing and then became constant in later stages. in Na2SO4–25%NaCl at 900 °C for (a) 100 cycles and (b) for initial 5
Because of the fluctuation in weight change during initial cycles
cycles in case of both nickel-based alloys, weight change
graph for first five cycles has been plotted separately as followed by weight gain till 5th cycle. After 5th cycle, both
shown in Fig. 2(b). It was observed that during initial 1st the specimens showed weight loss till 25th cycle and 65th
cycle, alloy 718 and alloy 600 both undergo weight loss cycle, respectively. Alloy 718 indicates minor gradual

123

weight gain till 60th cycle after that the weight change
becomes constant. However, overall weight change is very
low, while alloy 605 shows relatively higher weight gain
up to 35th cycle followed by weight loss till 65th cycle
after which the weight change became gradual.
SEM/EDS
The scanning electron microscopy (SEM) micrographs
showing the surface morphology of the specimens exposed
to the given molten salt environment at 900 °C for 100
cycles are presented in Fig. 3. Energy dispersive spec-
troscopy (EDS) analysis revealed the elemental composi-
tion of alloy 718, alloy 600, and alloy 605 after hot
corrosion for 100 cycles at 900 °C. Bare alloy 718 showed
formation of fragile oxide scale as can be seen from
Fig. 3(a) and (b). EDS analysis shows that the oxide scale
on the surface mainly contains oxygen, chromium, iron,
manganese, and nickel with minor amount of titanium. In
case of alloy 600 (Fig. 3c and d), almost similar spallad
oxide was observed throughout the surface. EDS analysis
Fig. 3 SEM micrographs along
with EDS for (a) and
(b) Superni 718, (c) and
(d) Superni 600 and (e) and
(f) Superco 605 after cyclic hot
corrosion in Na2SO4–25%NaCl
at 900 °C for 100 cycles
123
Metallogr. Microstruct. Anal.
shows the presence of chromium, nickel, and oxygen
thereby indicating the possibility of formation of NiCr2O4.
Substantial amount of manganese was also found in the
scale along with minor amount of iron. SEM image of bare
Superco 605 (Fig. 3e) shows that the oxide formed on the
surface has loose and porous scale at the top with an
adherent inner-oxide scale containing mainly cobalt,
nickel, and oxygen with minor amount of chromium. This
was after the spallation of the top layer. Figure 3(f) which
has been taken at higher magnification shows that the oxide
formed beneath the spallad surface was dense.
XRD
X-ray diffractograms of the oxide scale for alloy 718, alloy
600, and alloy 605 after hot corrosion for 100 cycles at
900 °C are shown in Fig. 4. NiO, Cr2O3, and NiCr2O4 are
the major oxide phases formed in the case of both Ni-based
alloys. Alloy 718 also indicated the formation of TiO2 and
Fe2O3, while alloy 600 shows some peaks of Mn3O4 and
Ni. In case of alloy 605, major peaks observed were CoO
Metallogr. Microstruct. Anal.
and CoNiO2. Figure 5 shows the x-ray diffraction analysis
of the spallad corrosion product fallen in the boat of alloy
605 during the hot corrosion run. The phases observed
from the analysis were Cr2O3, CoCr2O4, CoWO4, and
CoO.
Cross-Sectional Analysis
Figure 6 shows the back-scattered image of the cross sec-
tion of corroded alloys 718, 600, and 605 along with EDS
analysis at some points. Internal oxidation was observed in
the form of oxides penetrating into the substrate and along
the grain boundaries in all the three super alloys. The scale
formed on alloy 718 (Fig. 6a) was thick and adherent to
substrate, and there is an indication of oxide being present
in the substrate. Point 3 shows the presence of oxygen
along with chromium and nickel thereby indicating the
possibility of formation of spinel NiCr2O4 at the substrate
oxide interface. Points 4 and 5 which lie on the middle and
Fig. 4 X-ray diffractograms for Superni 718, Superni 600, and
Superco 605 after cyclic hot corrosion in Na2SO4–25%NaCl at
900 °C for 100 cycles
Fig. 5 X-ray diffractogram of
spallad materials present inside
the boat of alloy 605 after hot
corrosion in Na2SO4–25%NaCl
at 900 °C for 100 cycles
the top of the oxide scale, respectively, depicted the exis-
tence of major amount of oxygen, nickel, and iron along
with minor amount of chromium. For alloy 600 (Fig. 6b),
there seems to be penetration of the oxide through an
unoxidized layer, and the oxygen and sulfur have moved
along the grain boundaries deep in the substrate as can be
seen from point 3. This indicates the occurrence of sulfi-
dation. Existence of oxygen at point 4 depicted the
occurrence of internal oxidation as it lies in the substrate
region. Point 5 which lies on the substrate oxide interface
indicates the presence of oxygen and chromium thereby
showing the possibility of formation of chromium oxide.
Point 6 clearly revealed the presence of nickel and absence
of oxygen, indicating the presence of unreacted metal
within the oxide scale. Point 7 shows the existence of
oxygen, nickel, and chromium. In case of alloy 605
(Fig. 6c), scale is thick but at the substrate scale interface,
there was the presence of oxide scale and unreacted metal.
Internal oxidation has occurred at some points, and this
internal oxide has penetrated about 30 lm deep into the
substrate. Points 3, 4, 5, and 6 show the presence of cobalt
and oxygen along with nickel at points 5 and 6. This
indicates the possibility of formation of cobalt oxide
throughout the scale along with spinel of cobalt and nickel
in the top of the oxide scale.
X-ray Mapping
The elemental mapping of alloy 718 (Fig. 7) indicates the
presence of Cr and O at the substrate oxide interface
thereby indicating the possibility of formation of chromium
oxide. There was a thin layer of Mn present just below this
oxide layer. Oxygen was present in the rest of the scale
mainly with Fe and Ni with some amount of Cr and Mn.
The elemental analysis of alloy 600 (Fig. 8) indicates that
the formation of scale layers in between unreacted Ni
layers and the top layer consists of Cr and O with some Fe
and Mn. The Mn was also appeared with Cr in the top scale
and the bottom scale. Sulfur has penetrated below this scale
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Fig. 6 Cross-sectional analysis
for (a) Superni 718, (b) Superni
600, and (c) Superco 605 after
cyclic hot corrosion in
Na2SO4–25%NaCl at 900 °C
for 100 cycles
and was present in the substrate. Depletion of Cr and Mn
from the substrate was clearly seen. In case of alloy 605
(Fig. 9), the top scale consists of Co and Ni along with O
wherever Co and Ni are absent, and Cr was present. Just
above the substrate, there was a layer of oxide and unre-
acted metal. There was a penetration of oxide up to about
30 lm into the substrate perhaps along the grain boundary,
whereas in case of alloy 600, the sulfur has penetrated into
the substrate.
Discussion
Ni-based superalloys samples after hot corrosion for 100
cycles at 900 °C show greenish color which might be
attributed to the presence of Cr2O3 or NiO [26]. From
visual inspection, it was observed that very minute spall-
ation occured in both Ni-based alloys, whereas Co-based
alloy suffered from huge spallation in the form of flakes
and resulted in the thickness reduction of the substrate.
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Metallogr. Microstruct. Anal.
This catastrophic behavior of alloy 605 might be because
of the thermal expansion mismatch between the oxide scale
and the substrate. The presence of refractory material such
as tungsten also contributes to the poor resistance of the
alloy under the given environment [27].
Weight gain graph has been plotted to know the corro-
sion kinetics. It was observed that alloy 718 undergoes
weight loss during the initial cycle followed by very low
weight gain after 2nd cycle till 10th cycle, whereas alloy
600 shows very minor weight loss at 2nd cycle followed by
weight gain till 5th cycle. Minor gradual weight loss till
60th cycle was observed. The weight loss in case of both
the Ni-based alloys might be due to the volatile effect of
chlorides. Formation of CrO3 might have also contributed
to the loss in weight. This is because chromium oxides
(CrO3) or hydroxides are also volatile causing the weight
loss of these alloys and chromium depletion in the sub-
surface area [28]. But simultaneously the elements present
in the alloy are forming oxide on the surface. Hence, the
fluctuation in weight gain graph is due to the formation of
Metallogr. Microstruct. Anal.

Fig. 7 X-ray mapping analysis

for Superni 718 after cyclic hot
corrosion in Na2SO4–25%NaCl
at 900 °C for 100 cycles

123

Fig. 8 X-ray mapping analysis
for Superni 600 after cyclic hot
corrosion in Na2SO4–25%NaCl
at 900 °C for 100 cycles
oxides and evaporation of the metal chlorides simulta-
neously. After the formation of sufficient oxide on the
substrate, the weight again starts decreasing which may be
due to the dominating volatile effect of chlorine. The
chlorine present in the environment reacts with chromium,
aluminum, tungsten, and titanium present in the alloy, and
form highly volatile metal chlorides [23]. The metal
chlorides have low vapor pressure at the substrate oxide
interface, and thus change its state and diffuse toward the
top of the oxide in the form of gas. On the top of the scale,
these metal chlorides get converted into oxide and gaseous
chloride which evaporate in the form of gas leaving the
oxide unprotective. Oh et al. [27] reported the corrosion
behavior of a series of commercial superalloys in flowing
Ar–20%O2–2%Cl at 900 °C and observed that most of the
alloys exhibited decrease in mass due to the formation of
volatile chloride or oxychloride corrosion products. Chang
et al. [29] also discussed the occurrence of weight loss due
123
Metallogr. Microstruct. Anal.
to volatilization in the presence of chlorine in the envi-
ronment. In the present study, it was also observed that
after about 60 cycles, the weight change became nearly
constant in both the Ni-based alloys. This might be due to
the formation of NiO layer in alloy 718 which has higher
corrosion resistance as compared to chromium oxide in
chlorine environment [30]. Formation of spinels as well as
chromium oxide might have also contributed to the cor-
rosion protection after some cycles. Alloy 605 shows linear
weight gain because of the spallation behavior of the oxide
layer. But once the spallation of thick oxide layer begins,
the weight loss of the specimen also begins. After 70th
cycle, the weight of the specimen again started increasing
gradually thereby indicating the formation of new oxide
layer. Higher weight gain accompanied by severe spalla-
tion shows the susceptibility of cobalt-based alloy under
the environment containing sodium sulfate and sodium
chloride.
Metallogr. Microstruct. Anal.
Fig. 9 X-ray mapping analysis
for Superco 605 after cyclic hot
corrosion in Na2SO4–25%NaCl
at 900 °C for 100 cycles
The protective behavior of alloy 718 and alloy 600 as
compared to alloy 605 might be attributed to the formation
of NiO, Cr2O3, and NiCr2O4. The presence of Cr, Ni along
with O has been indicated in EDS (Fig. 3a and b) analysis
for both the specimens, and it was further confirmed by
XRD analysis (Fig. 4). A similar result has also been
reported for superalloys in Na2SO4–NaCl–K2SO4–KCl
environment [31]. Formation of NiO significantly contrib-
uted to the protection in the case of Ni-based alloys. It was
reported that oxides of Ni have low solubility in chloride
environment, whereas chromium dissolves in such condi-
tions [5, 32]. Moreover, when NiO formed on the top of the
oxide scale, it does not allow oxide of chromium to
evaporate thereby protecting the substrate.
123

XRD analysis also shows the formation of Fe2O3 in case
of alloy 600. This is due to the presence of iron in the
substrate which combines with oxygen to form iron oxide
when exposed to high temperature. Iron oxide can also be
formed on the top of the scale under the chlorine envi-
ronment as per the reactions (1)–(5). Penetration of chlo-
rine through the metal oxide scale to the oxide/metal
interface causes reaction with substrate elements to form
metal chlorides which have been described by Lee et al.
[33] with the following reactions shown in Eqs. (1) and (2):
Fe þ Cl2 ! FeCl2 ðsÞ ð1Þ
Fe þ 2HCl ! FeCl2 ðsÞ þ H2 ðgÞ: ð2Þ
Equation (3) shows the phase change of metal chloride
due to the high vapor pressure at the interface. Diffusion of
metal chloride vapor outward through the scale lead to the
formation of metal oxide and releasing of chlorine gas as
shown in Eqs. (4) and (5):
FeCl2 ðsÞ ! FeCl2 ðgÞ ð3Þ
3FeCl2 þ 2O2 ! Fe3 O4 þ 3Cl2 ð4Þ
2FeCl2 þ 1:5O2 ! Fe2 O3 þ 2Cl2 : ð5Þ
In XRD analysis, no peak of metal chloride was iden-
tified. This may be because of the reaction of the metal
chlorides as discussed earlier which ultimately lead to the
formation of metal oxides. Grabke et al. [34] suggested that
the chlorides in the deposit react with the scale thereby
releasing chlorine which enters into the scale and again
react with the substrate to form FeCl2(s) at scale/metal
interface. This evaporates as FeCl2(g), and after oxidation
converts into Fe2O3 at the scale surface and chlorine so
released either evaporates or again enters into the scale
which leads to the formation of porous and unprotective
scale. Deb et al. [24] also reported the reaction of NaCl
with oxides when Ni-based alloys exposed to 900 °C in
75% Na2SO4–25%NaCl molten salt environment under
isothermal condition. They reported that NaCl reacts with
the oxides releasing chlorine, which in turn reacts with the
oxides to form volatile chlorides:
2Cr2 O3 ðsÞ þ 6Cl2 ðgÞ ! 4CrCl3 ðgÞ þ 3O2 ðgÞ; ð6Þ
NiOðsÞ þ Cl2 ðgÞ ! NiCl2 ðgÞ þ ð1=2ÞO2 ðgÞ; ð7Þ
CrðsÞ þ 3=2Cl2 ðgÞ ! CrCl3 ðgÞ; ð8Þ
NiðsÞ þ Cl2 ðgÞ ! NiCl2 ðgÞ: ð9Þ
From Eqs. (6)–(9), it can be inferred that metal chlorides
evaporated from the oxide in the gaseous form thereby
leaving behind unprotective oxide. Tsaur et al. [22] sug-
gested that the formation of volatile species was respon-
sible for the observed decrease in weight of 310SS under
various ratios of Na2SO4/NaCl environment at 750 °C.
Hence, from the reported literature, it can be inferred that
123
Metallogr. Microstruct. Anal.
the presence of chlorine is mainly responsible for the
resulting weight loss as can be seen in the present study.
X-ray mapping of alloy 718 (Fig. 7) shows a thin band
of Cr, Mn, and O formed at the subscale region which was
assumed to be responsible for the protection of the sub-
strate from further damage. This layer also indicates the
possibility of formation of chromium oxide as can be
inferred from XRD analysis. The outer scale consists of Fe,
Ni, and O thereby indicating the formation of iron oxide
and nickel oxides. The Ni and Fe oxides on the top of the
scale hinder the Cr-oxides evaporation thus protecting the
substrate. Alloy 600 showed the formation of oxide con-
sisting of Cr, Mn, and O along with the sign of internal
oxidation. In literature [35], the oxidation study of alloy
600 and alloy 605 has been reported, where alloy 600
showed the formation of chromium oxide accompanied by
no internal oxidation which is responsible for providing
protection to the substrate at 900 °C. However, in the
study, it was suggested that chromium oxide has higher
tendency to dissolve in chlorine-containing environment
than the nickel oxide [30]. Hence, in the present study, the
chromium oxide formed might have dissolved due to the
presence of chlorine making the oxide unprotective and
lead to internal oxidation. Zahs et al. [36] in their study
reported the hot corrosion of Fe–15Cr and Fe–35Cr alloys
in N2–5 vol% O2 and He–5 vol% O2 with additions of
500–1,500 vppm HCl at temperatures between 400 and
700 °C. They reported the presence of iron and oxygen in
the outer layer of the scale and chromium along with the
oxygen in the subscale region. Similar formation of chro-
mium oxide was observed in the present study in case of
alloy 718 (Fig. 7). This shows that the thin oxide layer of
chromium which formed at the oxide substrate interface in
case of alloy 718 provides protection to the substrate after
some cycles in the given environment as no change in
weight was noticed after 60th cycle.
In the case of alloy 600, internal oxidation can be seen
as oxide penetrates below the thin layer of unreacted alloy.
Sulfur can also be seen in the substrate just below the
substrate scale interface as shown in cross-sectional ana-
lysis (Fig. 6b) point 3 and X-ray mapping (Fig. 8). Li
et al. [20] investigated single-crystal Ni-based superalloy
exposed to Na2SO4–25%NaCl at 900 °C and reported that
sulfur reacts preferentially with chromium and forms
internal sulfides beneath the oxide scale. Prescott et al. [37]
also reported the internal oxidation as well as weight loss in
case of six Ni- and Co-based superalloys in Ar–5.5% O2–
0.96% HCl–0.86% SO2 at 900 °C under isothermal and
thermal cycling condition. Zheng et al. [21] also found the
formation of sulfide during hot corrosion of powder met-
allurgy (PM) Rene95 Ni-based superalloy in molten
25%NaCl ? 75%Na2SO4 salts at 750 °C after 200 h.
Johnson et al. [12] reported the presence of internal sulfides
Metallogr. Microstruct. Anal.
in the form of CrS in cross section of Co–25Cr–7.5W
oxidized at 900 °C for 22 h in Na2SO4–40%NaCl salt
environment.
In the case of alloy 605, the observed higher corrosion
rate might be caused by the presence of refractory materials
such as tungsten (15%). Gurappa [22] has reported that
refractory alloying elements such as molybdenum, tung-
sten, and vanadium accelerate the hot corrosion rate by
several folds in the presence of Na2SO4 and NaCl. Oh et al.
[27] suggested that Ni- or Co-based alloys having high
refractory metal content show the highest rates of attack
under chloride environment at 900 °C under isothermal
condition. X-ray mapping of corroded alloy 605 indicates
that top layer consists of Co, Ni, and O, while subscale is
rich in Cr and O which is present in the form of thin oxide
layer along the substrate scale boundary. The presence of
CoO and CoNiO2 was depicted in XRD (Fig. 4) analysis.
This shows that Co and Ni ions diffuse faster toward the
outer layer of the scale to form oxide. Lund et al. [38]
reported that cobalt ions diffuse faster through an outer
oxide scale than chromium ions and also confirmed the
presence of CoO in outer layer in case of oxidized Co–Cr
Fig. 10 Schematic of proposed mechanism for (a) Superni 718, (b) Superni 600, and (c) Superco 605 after cyclic hot corrosion in Na2SO4–
25%NaCl at 900 °C for 100 cycles
alloys. Kofstad et al. [39] suggested that Co-based alloys
do not form continuous layer of Cr2O3 rather spinel of Co–
Cr dispersed in the CoO matrix. Fu et al. [40] also reported
the formation of CoO as outer scale along with chromium
sulfide and aluminum sulfide in subscale region when Co–
10Cr–5Al alloys exposed to 900 °C in 25%NaCl ?
75%Na2SO4 salt. In Fig. 10, an attempt has been made to
represent the mechanism proposed for alloy 718, alloy 600,
and alloy 605 after hot corrosion under molten salt at
900 °C. When alloy 718 exposed in corrosive salt envi-
ronment at high temperature, the elements from the sub-
strate diffuse toward the surface of alloy and react with
oxygen thereby forming metal oxides. These oxides might
be further reacting with the corrosive species such as
chlorine to form metal chlorides thereby reducing the
overall weight change. The metal chlorides so formed
penetrate into the oxide layer and precipitate oxides leading
to release of chlorine and formation of porous oxide. Alloy
718 (Fig. 10a) must have undergone severe internal oxi-
dation and resulted in the formation of Cr2O3 along the
substrate grain boundaries. A dense and thin layer of Cr
and O exists between the substrate and scale interface
123

indicating the formation of chromium oxide. Thin layer of
Mn was also observed along with Cr and O layer. For-
mation of NiO was observed throughout the oxide. In case
of alloy 600 (Fig. 10b), the elements from the substrate
must have diffused toward the surface and led to the for-
mation of oxides in the initial stages. The scale so formed
mainly consists of chromium, iron, and manganese. Below
the scale, there is unreacted metal below which again the
scale is existing. Sulfur has penetrated into the substrate,
but overall weight change is very small. Plausible mecha-
nism for alloy 605 is shown in Fig. 10(c). During initial
cycles of exposure, the elements from the substrate diffuse
toward the surface and form oxides. The oxide so formed
consists of cobalt, chromium, and tungsten. During the
course of corrosion run, the molten salt reacts with oxides
and damages the protective oxide in the form of spallation.
When a thick oxide scale spalled from the substrate, a new
oxide was formed consisting of cobalt and nickel. This
alloy does not develop significant internal oxidation, which
is a reason of poor adhesion of scale to Co-alloy surface
and the spallation.
Conclusion
The two Ni-based and one Co-based superalloys have been
subjected to hot corrosion under Na2SO4–25NaCl envi-
ronment which is close to the environment in incinerator
and bio-fuel-fired boilers. Most of the information avail-
able is regarding the isothermal behavior of these alloys
under the given environment, but here cyclic condition has
been chosen which is more severe. The Ni-based alloy 718
and alloy 600 showed a very marginal weight gain for 100
cycles at 900 °C. But in case of alloy 718, NiO is seen as
the major component of the scale and there is a formation
of thin Cr2O3 layer between the scale and the substrate.
This layer must be capable of stopping diffusion of cation
and anion species thereby stopping the further reaction,
whereas in case of Superni 600, the scale is thin and is
mainly of Cr2O3, and the reacting species has penetrated
through the metal layer and has reacted with the substrate.
So there is a thin layer of unattacked metal layer between
the top and scale just above the substrate. In case of Co-
based alloy, there is a enormous weight gain accompanied
with intense spalling due to non-protective nature of the
scale. The main constituents of the scale are oxides of
cobalt, chromium, and tungsten. The final scale consists of
only cobalt and nickel. It can be concluded from the results
that nickel-based alloys will be more suitable for this
environment as compared to cobalt-based alloy.
123
Metallogr. Microstruct. Anal.
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