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

sulphur-free gas, but substantially suppressed by SO2. Internal sul-
Due to the high operating temperature, the working environ- phidation and oxidation were also observed [2].
ment in waste-fired boilers is highly harsh. The heating surface Sulphurization and oxidation of iron, chromium, nickel, and
of a waste boiler is often prone to high-temperature corrosion in their alloys in chloridizing and oxidizing atmospheres are exam-
variable degrees. Material degradation is accelerated in this high- ples of hot-corrosion processes. The materials were exposed to
temperature, aggressively corrosive environment. A heat transfer the single salts of K2SO4 and KCl. The chlorine is formed through
pipe used in power plants and refineries is one of the components the reaction of KCl and O2. Solid metal chlorides are then formed
or equipment which is frequently prone to failure such as particu- which evaporates at high temperatures. The phase diagram of
larly high-temperature corrosion. Therefore, these pipes should be KCl and K2SO4 show in KCl and K2SO4 diagram [3]. In recent
resistant to high-temperature corrosion and oxidation in order to research, adding SO2 to Fe–9Cr and Fe–9Cr–0.5Si resulted in partial
increase lifetime of alloys at high-temperature. Normally, the tubes passivation by chromia production, but not on Fe–9Cr–2Mn. In
in this procedure are exposed to carbon-containing environments, sulphur-free gas, alloy carburization was widespread, but SO2 sig-
showing oxidation and carburization reaction. Low oxygen activi- nificantly reduced it. There was additional internal sulphidation
ties and relatively high carbon activities define many of these habi- and oxidation in order to improve high temperature oxidation
tats. The high temperature corrosion processes may comprise and hot corrosion resistance of alloys [4].
carburization, sulphurization or oxidation [1]. However, the phe- The objective of this research is to study the high temperature
nomena of corrosion or degradation of this case may be complex. corrosion of carbon steel used as boiler tube subjected to simulated
Therefore, their corrosion behavior should be intensively studied combustion atmosphere. In order to predict lifetime in service of
in order to extend the life time of the tubes in the simulated com- the carbon steel tube in simulated combustion atmosphere, the
corrosion kinetics and surface characterization of corroded sample
⇑ Corresponding author. will be carried out. The reaction mechanism can be further dis-
E-mail address: [email protected] (M. Boonpensin). 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 Materials Today: Proceedings 77 (2023) 1112–1115

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

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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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.

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