Materials Today: Proceedings 77 (2023) 1112–1115

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Materials Today: Proceedings

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High-temperature corrosion behavior of carbon steel subjected to

simulated combustion atmosphere
Piyorose Promdirek a, Mack Boonpensin b,⇑
a
High Temperature Corrosion Research Centre, Department of Materials and Production Technology Engineering, Faculty of Engineering, King Mongkut’s University of
Technology North Bangkok, 1518, Pracharat 1 Road, Wongsawang, Bangsue, Bangkok 10800, Thailand
b
Thailand Department of Tool and Die Engineering, Tool and Die Technology Center (TDTC), Faculty of Engineering and Architecture, Rajamangala University of
Technology Suvarnabhumi, Mueang Nonthaburi, Province Nonthaburi 11000, Thailand

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

Article history: This research aimed to study the high-temperature oxidation of carbon steel in simulated combustion
Available online 23 December 2022 atmosphere. The comparative oxidation rate of sample substrate carbon steel was experimentally inves-
tigated. The comparative high temperature oxidation rate studies were carried out using different atmo-
Keywords: sphere of gas and salt at 800 °C with different time 1, 25, and 100 hr. The kinetics of oxidation rate of
Oxidation carbon steel were established with weight change measurements. The oxidation rate was measured by
Combustion boiler the ratio of weight loss and quantity of gas and gas-salt atmosphere. The morphology surface of oxidation
Carburization
in form of spallation and peeling of unprotected oxidation and sulphurization. The structure morphology
Sulphidation
and chemical composition were characterized by Scanning Electron Microscopy (SEM) and X-ray diffrac-
tometry (XRD). The oxidation behavior was further discussed in this research.
Copyright Ó 2023 Elsevier Ltd. All rights reserved.
Selection and peer-review under responsibility of scientific committee of the 2022 Research, Invention
and Innovation Congress.

1. Introduction bustion atmosphere. Alloy sulphurization was extensive in

Due to the high operating temperature, the working environ-
ment in waste-fired boilers is highly harsh. The heating surface
of a waste boiler is often prone to high-temperature corrosion in
variable degrees. Material degradation is accelerated in this high-
temperature, aggressively corrosive environment. A heat transfer
pipe used in power plants and refineries is one of the components
or equipment which is frequently prone to failure such as particu-
larly high-temperature corrosion. Therefore, these pipes should be
resistant to high-temperature corrosion and oxidation in order to
increase lifetime of alloys at high-temperature. Normally, the tubes
in this procedure are exposed to carbon-containing environments,
showing oxidation and carburization reaction. Low oxygen activi-
ties and relatively high carbon activities define many of these habi-
tats. The high temperature corrosion processes may comprise
carburization, sulphurization or oxidation [1]. However, the phe-
nomena of corrosion or degradation of this case may be complex.
Therefore, their corrosion behavior should be intensively studied
in order to extend the life time of the tubes in the simulated com-
⇑ Corresponding author.
E-mail address: Mack.b@rmutsb.ac.th (M. Boonpensin).
sulphur-free gas, but substantially suppressed by SO2. Internal sul-
phidation and oxidation were also observed [2].
Sulphurization and oxidation of iron, chromium, nickel, and
their alloys in chloridizing and oxidizing atmospheres are exam-
ples of hot-corrosion processes. The materials were exposed to
the single salts of K2SO4 and KCl. The chlorine is formed through
the reaction of KCl and O2. Solid metal chlorides are then formed
which evaporates at high temperatures. The phase diagram of
KCl and K2SO4 show in KCl and K2SO4 diagram [3]. In recent
research, adding SO2 to Fe–9Cr and Fe–9Cr–0.5Si resulted in partial
passivation by chromia production, but not on Fe–9Cr–2Mn. In
sulphur-free gas, alloy carburization was widespread, but SO2 sig-
nificantly reduced it. There was additional internal sulphidation
and oxidation in order to improve high temperature oxidation
and hot corrosion resistance of alloys [4].
The objective of this research is to study the high temperature
corrosion of carbon steel used as boiler tube subjected to simulated
combustion atmosphere. In order to predict lifetime in service of
the carbon steel tube in simulated combustion atmosphere, the
corrosion kinetics and surface characterization of corroded sample
will be carried out. The reaction mechanism can be further dis-
cussed in this study.

https://doi.org/10.1016/j.matpr.2022.12.046
2214-7853/Copyright Ó 2023 Elsevier Ltd. All rights reserved.
Selection and peer-review under responsibility of scientific committee of the 2022 Research, Invention and Innovation Congress.
P. Promdirek and M. Boonpensin Materials Today: Proceedings 77 (2023) 1112–1115

2. Experimental procedure Table 2

Composition of each simulated flue-gas atmosphere.

2.1. Substrate material N2 O2 CH4 SO2

Bal. 10 % 10 % 1%
In present study, bare steel has been selected as substrate mate-
rial for corrosion test. The samples were cut from the boiler tubes
into rectangular shape with approximate dimensions of
20  20  3 mm. The samples were then ground with SiC until
1000 grit and finally cleaned by ultrasonic agitation. The chemical
composition of the substrate material as exhibited in Table 1 was
analyzed by emission spectrometer, showing carbon steel equiva-
lent as AISI 1006.

2.2. Corrosion kinetics and characterization

The corrosion rate of steels was conducted in different simu-

lated atmosphere at a temperature of 800 °C for exposure time of
1, 25, and 100 h. The simulated atmospheres were the gas mixture
as shown in Table 2 and the combination of gas mixture and salt
mixed with 74 %mol KCl + 26 %mol K2SO4. Subsequently, the
weight of corroded samples was measured with microbalance with
accuracy of 0.1 lg for calculating weight change. All scale formed
on the surface of the samples were also considered for weight
change measurement. Fig. 1. Comparison of the kinetics of bare steel after tested at temperature 800 °C
The physico-chemical characterization of oxide scale was finally 100 h at different simulation atmospheres.
examined by X-ray diffraction, SEM equipped EDS.

3. Results and discussion

The results of corrosion kinetics, showing weight change versus

time, in different simulation atmosphere was exhibited in Fig. 1.
The weight change increased with increasing time for all samples.
It seemed that the kinetics were parabolic for all conditions. The
oxidation reaction can be controlled by the diffusion mechanisms,
showing sluggish weight change with increasing time. The maxi-
mum weigh change of the oxidation rate was the sample corroded
in mixture of gas and salt. Fig. 2. Show Structure surface Samples Blank after tested at temperature 800 °C
For preliminary observation by optical microscope, the top sur- 100 hr (a.) N2-O2-CH4-SO2 (b.) N2-O2-CH4-SO2 and KCl + K2SO4 atmosphere.
faces of the sample corroded in different atmosphere showed irreg-
ularly sized nodule and different colour, possibly being different
oxide phase at several locations, as shown in Fig. 2.
The results of microstructure of corrode samples in cross sec-
tion view showed that Fe-oxide and Fe-carbide layer was found
in mixture containing gas (N2-O2-CH4-SO2 atmosphere). The thick-
ness of corrosion scale was approximately 1.5 mm as shown in
Fig. 3. In addition, EDS measurements taken at selected area on
the surface of the deposited oxide scale indicated a uniform com-
position with Fel-Cl-S-O as major element also shown in Fig. 3.
The presence of Fe content (48.8 %), O content (36 %) and C content
(15 %) has been observed in the oxide surface, leading to the forma-
tion of carbides and oxides in the outer surface.
In N2-O2-CH4-SO2 environment the effect of SO2 is attributed to
the formation of a thin sulphate film on the oxide surface that
impedes Fe volatilization and decreases the rate of oxygen reduc-
tion on the oxide surface. In N2-O2-CH4-SO2 environment the cor-
rosion mitigating effect of SO2 is mainly attributed to the rapid
conversion of KCl to K2SO4. Fig. 3. Cross-section observation of corroded sample after tested at temperature
When mixture containing gas and salt (N2-O2-CH4-SO2 and KCl- 800 °C for 100 h in N2-O2-CH4-SO2 atmosphere by SEM.
K2SO4 atmosphere) was studied, the corrode surface was associ-

Table 1
Chemical composition of steel before corrosion test by emission spectrometer.

Fe C Mn Cu P S Si Cr Ni Mo
Bal. 0.064 0.338 0.186 <0.0005 0.004 0.246 0.057 0.094 0.014

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P. Promdirek and M. Boonpensin
ated with the melting temperature (303 °C) of the binary KCl + K2-
SO4 mixture [5]. It seemed that the corroded sample tested in the
mixture of gas and salt depicted a Fe-oxide and Fe-S layer in the
surface microstructure. After corrosion test at 800 °C for 100 h, it
showed that the corrosion scale was separated in different layer
and the corrosion thickness was approximately 1 mm. The Fe + C
l + S + O rich oxide layer of steel can be confirmed by EDS. Result
of the oxidation tested for samples after 100 h showed that the oxi-
des layer is fractured from some elements such as S and Cl that
enters the oxide layer shown in Fig. 3. The formation of sulfide
and carbide in the oxide scale, especially between oxide layer,
can lead to separation of each layer of the oxide scale due to the
more brittle phase than other phase.
The phases constitution analyzed from the XRD pattern on the
surface of corroded samples as presented. Fig. 5. The XRD analysis
for all samples indicated that the formation of Fe-S-Cl-O compound
was occurred on the corroded surface. From the XRD result as
shown in Fig. 4, the fine Fe2O3 and Fe3O4 were also occurred on
the surface of corroded steel after corroded at 800 °C for 100 h in
N2-O2-CH4-SO2. There were also KCl, Fe3O4 on the corroded surface
and possibly FeS in the inner layer of oxide scale, caused from
result of EDS examination in the crack surface of oxide scale. Due
to higher reaction rate of sulfidation and more defect formation
in oxide scale, sulfur easily diffused in the oxide scale, leading to
the crack propagation with brittle materials.
The samples steel showed the performance against this oxida-
tion process. It showed similarly formation of Fe-oxide and Fe-S
attack structure at two different environments in the microstruc-
ture. However, the existence of S and C played an important role
to accelerate the crack propagation in the inner layer of oxide scale.
In N2-O2-CH4-SO2 environment the effect of SO2 is attributed to
the formation of a thin sulphate film on the oxide surface that
impedes Fe volatilization and decreases the rate of oxygen reduc-
tion on the oxide surface. In this environment the corrosion miti-
Fig. 4. Cross-section observation of corroded samples after tested at temperature 800 °C for 100 h in N2-O2-CH4-SO2 and KCl-K2SO4 atmosphere by SEM.
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Materials Today: Proceedings 77 (2023) 1112–1115
gating effect of SO2 is mainly attributed to the rapid conversion
of KCl to K2SO4 [6].
The observations for the ternary Fe + KCl + K2SO4 mixture dif-
fered from the results of microstructure examination, showing
Fe2O3, Fe3O4 with C rich and FeS. The computations supported
observations of FeS, Fe3O4 and Fe2O3 formation in the ternary Fe-
KCl-K2SO4 mixture [7]. Although Fe2O3 and Fe3O4 is known to
lower the initial melting temperatures in combinations containing
K2SO4 and O2. The continual feeding of KCl via fly ashes to deposits
on superheater tube surfaces might be considered during simula-
tion atmosphere. In this case, the ability of KCl + K2SO4 to lower
the eutectic temperature could be critical in accelerating oxidation.
This corrosion morphology is referred to hot corrosion as Type B
which is concerned with the melting salt on the surface. The corro-
sion of melting salt occurred locally under the oxide layer. This cor-
rosion is one of non-uniform attack with pits of different sizes
growing into the metal [8].
4. Conclusion
The study of high-temperature corrosion of carbon steel in dif-
ferent simulated environments can be concluded as follows:
1. The weight change increased with increasing time for all sam-
ples. The corrosion kinetics were parabolic for both conditions.
This samples showed a higher oxidation rate at simulated
atmosphere with salt more than that in gas without salts.
2. The calculations and result of microstructure confirmed the for-
mation of FeS, FeO, Fe3O4, and Fe2O3 in the Fe-KCl-K2SO4 tern-
ary mixture. FeO, Fe2O3 and Fe3O4 were however found on the
surface of corroded steel in the simulated atmosphere without
salts.
3. The formation of sulfide and carbide in the oxide scale, espe-
cially between oxide layer, can lead to the separation of each
layer of the oxide scale due to the brittle phase of those phase.
P. Promdirek and M. Boonpensin Materials Today: Proceedings 77 (2023) 1112–1115

Fig. 5. Show XRD surface analysis Samples Blank after tested at temperature 800 °C 100 hr (a). bare steel (b). N2-O2-CH4-SO2 (c.) N2-O2-CH4-SO2 and KCl + K2SO4 atmosphere.

Data availability
Data will be made available on request.
Declaration of Competing Interest
The authors declare that they have no known competing finan-
cial interests or personal relationships that could have appeared
to influence the work reported in this paper.
Acknowledgements
This research was funded by High temperature corrosion cen-
ter, department of materials and production technology engineer-
ing, King Mongkut’s University of Technology North Bangkok.
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