Fresenius J Anal Chem (1998) 361 : 540–544 © Springer-Verlag 1998

CONFERENCE CONTRIBUTION

H. Nickel · Y. Wouters · M. Thiele · W. J. Quadakkers

The effect of water vapor on the oxidation behavior of 9%Cr steels

in simulated combustion gases

Received: 15 July 1997 / Revised: 5 February 1998 / Accepted: 10 February 1998

Abstract The effect of the O2 and H2O content on

the oxidation behavior of the 9%Cr steel P91 was studied
in the temperature range of 600–800 °C. The oxidation
rates under the various experimental conditions were de-
termined by in-situ thermogravimetry. In dry oxygen a
protective scale growth occurs with an oxidation rate
controlled by diffusion in the scale. In presence of water
vapor, after an incubation period, the scales become
non-protective, as a result of a change of the oxidation
limiting process. The water vapor effect is especially ap-
parent in the temperature range of 600–700 °C, whereas
at higher temperatures hardly any effect was found. The
destruction of the protective scale by water vapor does
not only depend on the H2O content but also on the
H2O/O2-ratio.
Fig. 1 Oxidation of 9 and 12%Cr (X20) steels in a simulated com-
bustion gas (SCG) and air at 650 °C
1 Introduction

In power plants, 9%Cr steels are being discussed as con-

struction materials for piping, headers and superheater
tubes [1–3]. For these materials, the challenge is to find a
compromise between optimum mechanical properties and
corrosion resistance. During the last years, a number of
studies have been carried out concerning the thermal oxi-
dation of 9%Cr steels in simulated combustion gases of
coal fired plants which usually contain O2, H2O, CO2,
SO2, NO2, HCl. The studies have shown [4], that, in con-
trast to 12%Cr steels, 9%Cr steels possess in the simu-
lated combustion gases an oxidation resistance which is far
worse than in air (Fig. 1). It was recently proposed that the
gas component which is mainly responsible for the rapid
oxidation in the combustion gases is water vapor [4, 5]. In
fact, a harmful effect of water vapor on the oxidation re-
sistance of FeCr alloys has been reported several years
H. Nickel1 (Y) · Y. Wouters · M. Thiele · W. J. Quadakkers
Forschungszentrum Jülich GmbH,
Institute for Materials in Energy Systems (IWE 1),
D-52425 Jülich, Germany
1 also Technical University Aachen (RWTH)
ago. Alloys which exhibit protective behavior in dry oxy-
gen can show a sort of breakaway oxidation in wet gases.
Although this process of protective scale destruction has
been reported by several authors [6, 7], a conclusive
mechanism has not been elucidated.
Therefore in the present work a study was carried out
to clarify the effect of various oxidation parameters (tem-
perature, O2 content, H2O content) on the oxidation be-
havior of the 9%Cr steel P91.
2 Experimental
The chemical composition of the steels studied were given in [4].
Rectangular specimens 20 × 10 × 2 mm in size were ground to 800
grit surface finish prior to the exposure in simulated combustion
gases consisting of 1 vol% O2, 14 vol% CO2, 0.1 vol% SO2,
0.01 vol% HCl (Rest N2) and a water vapor content of 7%. The ex-
posures were carried out for up to 10 000 h at 650 °C whereby the
specimens were cooled to room temperature every 250 h for weight
measurements. Mechanistic investigations were carried out in N2-
1%O2-x%H2O model gases using a Seteram thermobalance which
allowed in-situ gas changes during isothermal oxidation without

intermediate cooling. After exposure the corrosion products were
analyzed by optical metallography, scanning electron microscopy
(SEM), energy dispersive X-ray analysis (EDX), X-ray diffraction
(XRD) and secondary ion mass spectrometry (SIMS).
Fig. 2 a–c Thermal oxidation of P91 in N2-1%O2-x%H2O mix-
tures at 650 °C
Fig. 3 a, b Oxide scales on P91 after oxidation in a) N2-1%O2,
250 h at 650 °C (SEM observation), b) N2-1%O2-2%H2O, 100 h at
650 °C (optical metallography)
541
3 Results
Figure 2 presents the weight change data obtained for P91
during isothermal oxidation in an N2-1%O2 gas with dif-
ferent H2O contents at 650 °C. In the dry gas, an ex-
tremely slow oxidation rate occurs which is close to para-
bolic. After 25 h, the total specific weight gain is only
about 5 µg/cm2, a value close to the detection limit of the
used thermobalance. The SEM analysis of a sample after
250 h of oxidation under the same conditions shows a thin
oxide layer with a thickness of about 1 µm, appearing
compact and adherent (Fig. 3). The EDX analysis reveals
that the scale mainly consists of iron, chromium and mi-
nor amounts of manganese, molydenum and silicon (see
Table 1). With X-ray diffraction only the Fe2O3 structure
could be detected.
In the wet environments a very high oxidation rate oc-
curred after an initial incubation period, which is a func-
tion of H2O content (Fig. 2). In the incubation period the
kinetics show a parabolic growth rate which is slightly
higher than in the dry gas. After the incubation period the
curves follow a linear rate with a rate constant which de-
pends on the H2O content (see Fig. 2 c). The microscopic
observations of the specimens oxidized in the wet gases
Table 1 EDX analysis of scale on P91, compared with bulk alloy
composition, after 250 h oxidation in N2-1%O2 for 250 h at 650 °C
(compare Fig. 3 a)
Element Alloy (Atom %) Oxide layer (Atom %)
Fe 88 73.2
Cr 9.6 20.4
Si 1.2 0.5
Mo 0.5 1.4
Mn 0.7 4.5
Fig. 4 SIMS profile of oxide scale (tapered cross section) on P91
oxidized in an N2-1%O2-2%H2O mixture at 650 °C for 7 h
542
Fig. 5 Influence of water vapor on the rate of oxidation of P91 in
N2-1%O2-x%H2O mixtures between 600 and 800 °C
Fig. 6 Metallographic cross sections of P91 after 100 h oxidation in N2-1%O2-4%H2O at different temperatures
show porous scales which consist of three parts identified
as Fe2O3 (outer), Fe3O4 (middle) and (Fe,Cr)3O4 (inner)
(Fig. 3). This information is confirmed by the SIMS line
scan (see Fig. 4) determined on a tapered cross section,
which shows in the internal part of the scale a chromium
enrichment, whereas in the outer part no chromium is pre-
sent.
The enhancement of the oxidation by the presence of
water vapor does not continuously increase with tempera-
ture (Figs. 5, 6). For 2 and 4% of H2O, a bell shape tem-
perature dependence is recorded with respective oxidation
rate maxima at 650 and 700 °C. At 800 °C, however, a
protective scale is formed, irrespective of the H2O content
(0, 2 and 4%) in the gas. Consequently, at a given H2O-
content of 4% the oxidation rate in the temperature range
650–800 °C decreases with increasing temperature (Fig.
6). Figure 7 shows results of thermogravimetric (TG)
analyses at 650 °C whereby the gas was cycled between

Fig. 7 Specific weight gain during isothermal oxidation of P91 at
650 °C during in-situ change of test gas from wet to dry and vice versa
Fig. 8 Isothermal oxidation of P91 in N2-O2-H2O mixtures at 650 °C
wet and dry N2-1%O2. It appears that in experiments,
which started in wet gas, the oxidation rate immediately
changes upon changing the test atmosphere. However,
when the exposure was started in the dry gas, no increase
of the oxidation rate was observed upon changing to the
wet environment.
Figure 8 presents the kinetic data obtained during
isothermal oxidation of P91 samples at 650 °C in N2-O2-
x%H2O mixtures (x = 2% and 4%), which in contrary to
the previous experiments contain 2% oxygen. The
recorded kinetics are similar to those obtained in dry oxy-
gen, i.e., no enhanced oxidation occurs in spite of the
presence of water vapor. Apparently, an increase of the
543
O2 content from 1 to 2% suppresses the detrimental effect
of H2O if present in the given concentrations.
4 Discussion
In literature [7, 8] a number of mechanisms have been
proposed to explain the destruction of the protective scale
on Fe-Cr-alloys due to the presence of water vapor [4]:
1. formation of volatile Cr-oxihydroxides or 2. Fe-hy-
droxides, 3. enhanced surface reaction kinetics, 4. proton
defects in the oxide lattice and 5. formation of oxygen
bridges by H2O/H2-mixtures in oxide pores. The last men-
tioned mechanism was proposed to explain the H2O effect
on the growth rate of thick porous oxide layers on pure
Fe, and therefore seems unlikely to be responsible for the
breakdown of the very thin scales discussed here. Mecha-
nism 1 is unlikely according to results, which showed that
the protective properties of the scale formed in dry gas are
retained up to at least 100 h upon switching to wet gas
(Fig. 7). Enhanced oxidation due to the formation of
volatiles Fe-hydroxides also seems to play only a minor
role, because TG studies with pure Fe showed hardly any
effect of water vapor content on oxidation kinetics [9].
This result also makes mechanism 3 quite unlikely.
All the results obtained in the present study seem to be
in favor of a kinetic effect of water vapor. The collected
informations in the literature about the iron-rich oxide
(Fe,Cr)2O3, which forms in dry gas, indicate that this ox-
ide is very close to stoichiometry, and some studies have
shown that the major point defects in the lower tempera-
ture range (T < 800 °C) are oxygen vacancies. The modi-
fications caused by the presence of water vapor are not re-
lated to the nature of the protective scale, which remain the
same as shown by the X-ray diffraction after oxidation at
different temperatures. However, as previously found in
the case of some pure metals [10, 11] the presence of water
vapor can change the nature of point defects and conse-
quently the diffusion process. In wet gases the oxide de-
fect structure can be altered due to the presence of a sub-
stitutional hydroxide in the scale. Presence of such a
species is in good agreement with very recent studies con-
cerning the water vapor effect on pure metal oxidation
[10]. Due to its smaller size (0.095 nm) compared to the
O2– ion (0.140 nm) the substitutional hydroxide diffuses
faster in the scale and leads to an increase of the oxidation
rate. In the present conditions the rate is related to the ra-
tio H2O/O2 which determines the relative content of OH
groups in the scale. If the H2O/O2 ratio is high, the amount
of the substitutional hydroxide is high leading to a high
growth rate. This has as a consequence that the amount of
Cr, which can be supplied by the alloy to the scale, is too
low to retain the optimum Cr content in the (Fe,Cr)2O3.
Apparently, a minimum amount of Cr is necessary to
stabilize the protective (Fe, Cr)2O3 structure thereby pre-
venting the formation of rapidly growing Fe3O4. Possibly,
the mentioned M2O3 oxide results due to a transformation
from an initially formed Cr-rich, (FeFexCr2–x)O4 as pro-
posed by some authors. The large increase of the oxida-
544
tion rate after the breakdown of the protective (Fe,Cr)2O3
leads to a completely different scale morphology. The
SEM observations have shown a large porosity through-
out this Fe3O4-rich scale (Fig. 3 b). This observation in
combination with the kinetic data leads to the proposal
that in case of this non-protective scale the internal inter-
face might be the place of the limiting process of oxida-
tion with competition between the decomposition of the
two species O2 and H2O. These assumptions explain the
dependence of the rate of oxidation from the O2 and H2O
content after the breakdown (Fig. 7).
In the TG analyses at 650 °C whereby the gas was cy-
cled between wet and dry (Fig. 7) beginning by a wet one,
the presence of water vapor leads rapidly to a rate of oxi-
dation which is a function of both O2 and H2O contents,
with a competition between reactions at the internal inter-
face. When the atmosphere is changed to dry, the decrease
of the oxidation rate can be explained to be the conse-
quence of the new growth of an (Fe,Cr)2O3-based protec-
tive layer at the alloy/scale interface. This assumption is
in good agreement with the fact that an incubation period
is observed upon a new change of the atmosphere from
dry to wet (Fig. 7). Concerning the kinetic curves recorded
in a cycled atmosphere beginning by a dry gas, the expla-
nation is less obvious. The rate of oxidation after 2 h in
dry gas remains approximatly constant when the atmo-
sphere is changed from the dry to the wet atmosphere.
This could be related to the fact that the protective oxide
formed in the dry gas slightly differs in composition, e.g.
Cr content, compared to that initially formed in the wet
gas. An indication for this difference can be derived from
the growth rates of the protective scales, which were
slightly higher in the wet gas than in the dry gas (Fig. 2).
5 Conclusions
The results presented have confirmed, that the oxidation
of 9%Cr steels is strongly affected by water vapor. How-
ever, the type and rate of oxidation, as well as the compo-
sition and morphology of the oxide scales do not only de-
pend on the H2O content in the oxidizing atmosphere but
also on the H2O/O2-ratio. At low contents of H2O and
high contents of O2 a slow parabolic law is observed with
the scale growth being controlled by diffusion through a
scale with a composition (Fe,Cr)2O3. At high contents of
H2O and low contents of O2 the oxidation initially also
starts with a parabolic law, however with a slightly higher
rate than in dry gas. The oxidation rate during the first
hours of oxidation is a function of the ratio H2O/O2, prob-
ably as a result of the contribution of substitutional hy-
droxide to scale growth. The higher growth rate in the gas
with high H2O/O2 ratios eventually leads to a breakdown
of the protective scale. This is followed by an approxi-
mately linear oxidation of an Fe3O4-rich scale in which
the rate is probably controlled by a competition of reac-
tions between O2 and H2O at the internal interface. The
rate of Cr incorporation into the scale is then determined
by Cr diffusion in the alloy.
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