Oxid Met (2011) 76:111–126

DOI 10.1007/s11085-010-9227-1

ORIGINAL PAPER

HCl-Induced High Temperature Corrosion of Stainless

Steels in Thermal Cycling Conditions and the Effect
of Preoxidation

P. Viklund • R. Pettersson

Received: 19 April 2010 / Revised: 29 September 2010 / Published online: 19 December 2010
Ó Springer Science+Business Media, LLC 2010

Abstract Gaseous HCl released during combustion is one reason for the severe
materials degradation often encountered in power generation from waste and bio-
mass. In this study, three stainless steels (the low alloyed EN 1.4982, the standard
EN 1.4301 and the higher alloyed EN 1.4845) were tested by repeated thermal
cycling in an environment comprising N2–10%O2–5%H2O–0.05%HCl at both 400
and 700 °C. The materials were exposed with ground surfaces and preoxidised at
400 or 700 °C. A positive effect of preoxidation is evident when alloys are exposed
at 400 °C. Oxide layers formed during preoxidation effectively suppress chlorine
ingress for all three materials, while chlorine accumulation at the metal/oxide
interface is detected for surface ground specimens. The positive effect of preoxi-
dation is lost at 700 °C and corrosion resistance is dependent on alloying level. At
700 °C metal chloride evaporation contributes significantly to the material degra-
dation. Based on the results, high temperature corrosion in chlorinating environ-
ments is discussed in general terms.

Keywords High temperature corrosion  Stainless steel  Preoxidation  HCl 

Thermal cycling

Introduction

At elevated temperatures, metals and alloys are dependent on the formation of a

protective oxide scale to prevent material degradation. Scales of Cr2O3, Al2O3 or
SiO2 are regarded as protective, and materials designed for high temperature

P. Viklund (&)
Swerea KIMAB AB, P.O. Box 55970, 10216 Stockholm, Sweden
e-mail: peter.viklund@swerea.se

R. Pettersson
Outokumpu Stainless AB, P.O. Box 74, 77441 Avesta, Sweden

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112 Oxid Met (2011) 76:111–126

applications are alloyed with chromium, aluminium or silicon to minimise the

corrosion damage.
One degradation phenomenon of considerable technological interest is high
temperature corrosion in oxidising-chlorinating environments. A growing interest in
burning renewable fuels has further emphasised the need to mitigate this type of
chlorine-induced corrosion. Combustion of waste, and to some extent also biomass,
releases high levels of gaseous HCl which is considered a primary reason for the fast
corrosion of critical components such as superheater tubes. Despite numerous
studies on the oxidation-chlorination of both pure metals [1–5] and alloys [4–8], the
mechanisms behind the breakdown are still under debate. The term ‘‘active
oxidation’’ is frequently used to describe corrosion in the presence of poorly
protective oxide scales [2–6, 8]. The role of chlorine is often explained by the so-
called ‘‘chlorine-cycle’’ [5]. This mechanism involves inward diffusion of molecular
chlorine to the metal/oxide-interface where metal chlorides (predominantly FeCl2
on ferritic and austenitic steels) are formed. As temperatures are rather high, these
metal chlorides will evaporate and diffuse outwards towards the gas phase. When
reaching regions with higher oxygen partial pressure the metal chlorides are
destabilised and will transform into metal oxides, releasing chlorine that causes
further attack and thereby closing the chlorine-cycle.
In this paper the effect of preoxidation on the HCl-induced high temperature
corrosion is investigated for three commercial austenitic stainless steel grades; EN
1.4982 with a high manganese content but fairly low in chromium, the standard EN
1.4301 and the higher alloyed EN 1.4845. Specimens were exposed with ground
surfaces and after preoxidising at 400 or 700 °C. Exposures were conducted during
repeated thermal cycling in an oxidising chlorinating environment at both 400 and
700 °C.

Experimental Set-Up

Two different exposures, according to Table 1, were conducted in an environment

comprising N2–10%O2–5%H2O–0.05%HCl at 400 and 700 °C respectively. The
thermal cycling (Fig. 1) consisted of a 20 h hot dwell time and a 4 h cold dwell time
at room temperature. The 400 °C exposure comprised 49 cycles and a total hot
dwell time of 980 h, while the 700 °C exposure lasted for 280 h with 14 cycles
down to room temperature.
Experiments were carried out in a modified, Xerion tube-type furnace. The
furnace is constructed to allow supply of both liquid and gaseous substances. A gas

Table 1 Experimental conditions used for the exposures

Temperature Bal. O2 H2O HCl Cycles Hot dwell
(°C) (vol.%) (vol.%) (vol.%) time

Series 400 °C 700 N2 10 5 0.05 14 980 h

Series 700 °C 400 N2 10 5 0.05 49 280 h

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Fig. 1 The temperature cycling during exposures with a hot dwell time of 20 h and cold dwell time
of 4 h

flow of 143 mL/min was used for the N2/O2—mixture while H2O and HCl were
supplied as hydrochloric acid via a peristaltic pump and vaporized within the tube.
The flow rate of gaseous HCl/H2O was approximately 7.5 mL/min inside the tube.
The furnace was slightly inclined to drain away condensed species from the area
containing the specimens. A fan system and a movable furnace allows for rapid
cooling.
The exposed materials are three commercial austenitic grades with compositions
according to Table 2. All specimens were prepared by wet grinding with 600 mesh
silicon carbide paper and thoroughly cleaned in ethanol prior to exposure. The
alloys were exposed both in the ground surface condition and after preoxidation for
24 h in synthetic air at 400 or 700 °C. During exposure each specimen was placed
in an individual alumina crucible.
After exposure gross and net mass changes as well as the amount of spalled oxide
were recorded on a balance with sensitivity of ±0.01 mg. Loosely adherent oxide
scales were removed by gently tapping the test piece on the inside of the alumina
crucible, using a tweezers, to ensure that the spalled oxide is collected. Post
exposure analyses were performed using Glow Discharge Optical Emission
Spectroscopy (GDOES), X-Ray Diffraction (XRD) and Scanning Electron Micros-
copy (SEM). Thermodynamic calculations were made with HSC v.4.1 and the
SSUB3 and TCFE5 databases in ThermoCalc R.

Table 2 Composition of the investigated materials in weight percent

Material Fe Cr Ni Si Mo Mn C N Others

EN 1.4982 Bal. 15.5 9.24 0.54 1.06 6.3 0.077 1.04Nb, 0.25 V
EN 1.4301 (AISI 304) Bal. 18.15 8.44 0.35 0.41 1.74 0.015 0.069
EN 1.4845 (AISI 310S) Bal. 25.06 19.36 0.56 0.13 0.99 0.046 0.038

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Results

Preoxidation in Synthetic Air

Materials were preoxidised in synthetic air for 24 h at 400 and 700 °C respectively
and the oxides analysed with GDOES, SEM and XRD. Elemental depth profiles
were performed on all preoxidised specimens and the results are summarised in
Table 3.
The oxides formed during preoxidation were 0.05–0.2 lm thick, and had a
chromium content which increased with the chromium content in the alloy. The
oxide chromium content also increased with preoxidation temperature, as is to be
expected due to higher diffusion rates of Cr at elevated temperatures [9]. While
iron-oxides are known to provide poor corrosion resistance, a corundum-type oxide
(M2O3) rich in chromium is regarded protective with low ionic conductivity. Spinel-
type oxides (M3O4) are frequently observed on high alloyed steels, but are
considered less protective than the corundum-type oxide [10–12]. According to
XRD-analyses M2O3 dominates the scale formed at 700 °C with only little spinel-
type oxide present. At 400 °C the oxide scales were much thinner, rendering it more
difficult to accurately determine oxide structure. However, it seems that M2O3
predominated in this case as well. A GDOES depth profile of 1.4845 preoxidised at
400 °C is presented in Fig. 2, and shows an outer iron-rich oxide and an inner oxide
enriched in chromium.
Combining the results from XRD and GDOES it seems that oxide composition
on the preoxidised specimens ranges from Fe1.5Cr0.5O3 (1.4982 preoxidised at
400 °C) to Fe0.3Cr1.7O3 (1.4845 preoxidised at 700 °C). The preoxidised materials
thus show vast differences in oxide composition, even though all three steel grades
are austenitic chromia formers.

Exposure in HCl-Containing Atmosphere at 400 °C

Gross and net mass changes, as well as cumulated spall, after 49 cycles (980 h), are
shown in Fig. 3 for all three stainless steel grades. Small mass changes are evident,
as a comparison, carbon steel with a ground surface which was exposed under the

Table 3 Properties of the oxides formed during preoxidation

Material Oxide thickness Maximum Cr/(Cr ? Fe ? Oxides according
(\5% O in Ni ? Mn)-ratio to GI-XRD
GDOES, lm) in the oxide (GDOES)

1.4982, PO at 400 °C 0.1 0.25 M3O4, M2O3

1.4982, PO at 700 °C 0.4 0.27 M3O4, M2O3 (strong signal)
1.4301, PO at 400 °C 0.05 0.31 M2O3*
1.4301, PO at 700 °C 0.2 0.57 M3O4, M2O3 (strong signal)
1.4845, PO at 400 °C 0.05 0.65 M2O3*
1.4845, PO at 700 °C 0.2 0.84 M3O4, M2O3 (strong signal)

* Thin oxide scales leading to low intensity

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Fig. 2 GDOES depth profile of 1.4845 preoxidised 24 h at 400 °C in synthetic air

Fig. 3 Gross and net mass changes and cumulated spall of the investigated materials after 980 h hot
dwell time at 400 °C and 49 cycles down to room temperature

same conditions exhibited a gross mass gain of 0.45 mg/cm2. Some oxide spallation
was detected for all three materials, so the net mass changes could be either positive
or negative. The difference between the three alloys is small, indicating that
alloying level is not the primary factor governing corrosion resistance. Instead, it
seems that the initial surface condition determines alloy performance. Both the
gross mass change and the amount of cumulative spall are lowest for specimens
preoxidised at 400 °C and highest for the surface ground specimens.
In Fig. 4 the amount of cumulated spall for 1.4982 during the exposure is shown.
The beneficial effect of preoxidation is evident after the first cycle and is maintained
throughout the exposure. The lowest amount of cumulated spall was seen for
specimens preoxidised at 400 °C.

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Fig. 4 Cumulated spall of the 1.4982 specimen during the 980 h cyclic exposure at 400 °C

Analyses of the corrosion products, Table 4, show that the preoxidised samples
maintained a higher chromium content in the oxide, which correlates to the very
limited spallation. Another clear difference between the specimens was chlorine
accumulation at the metal/oxide interface for all three alloys with ground surfaces.
Chlorine accumulation at the metal/oxide interface was not detected on any of the
preoxidised specimens and this behaviour is illustrated by GDOES compositional
depth profiles in Fig. 5. The result provides evidence that chlorine diffusion through
a dense oxide scale is very limited. This behaviour is apparent even in cases when
the oxides contain low chromium levels (1.4982).
SEM examination showed metal chlorides scattered over the surface, Fig. 6, in
agreement with the elevated surface chlorine levels seen in Fig. 5. The chlorides
were detected on both surface ground and preoxidised specimens. Different chloride
morphologies were observed, with both blisters and protrusions.

Table 4 Summary of the corrosion products formed after exposure at 400 °C (980 h)
Material Oxide thickness Max. Cr/(Fe ? Cr ? Cl accumulation at
(\5% O in GDOES, lm) Mn ? Ni) ratio metal/oxide interface
in the oxide

4982 0.33 0.11 Yes

4982, PO at 400 °C 0.18 0.13 No
4982, PO at 700 °C 0.42 0.29 No
4301 0.43 0.24 Yes
4301, PO at 400 °C 0.04 0.51 No
4301, PO at 700 °C 0.16 0.6 No
4845 0.16 0.44 Yes
4845, PO at 400 °C 0.16 0.64 No
4845, PO at 700 °C 0.27 0.7 No

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Fig. 5 Depth profiles showing the accumulation of chlorine beneath the oxide for ground surface
specimens but not for those which were preoxidised. The behaviour is evident for both the low-alloyed
1.4982 (a) and the higher alloyed 1.4845 (b)

Fig. 6 Appearance of the 1.4301 ground surface specimen exposed for 980 h at 400 °C in an
environment comprising N2–10O2–5H2O–0.05HCl. Metal chlorides are frequently detected on the metal
surface both as blisters (a) and as protrusions (b)

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Exposure in HCl-Containing Atmosphere at 700 °C

Gross- and net-mass changes, as well as cumulated spall, after 280 h of exposure
and a total of 14 cycles down to room temperature are shown in Fig. 7. Carbon steel
with a ground surface exposed under the same conditions exhibited a gross mass
gain of 89 mg/cm2. In contrast to the exposure at 400 °C, no beneficial effect of
preoxidation is seen for any of the three stainless steel grades. It is possible that the
thicker scales formed during exposure at 700 °C are more prone to cracking and
spallation due to stress caused by the thermal cycling. If so, the positive effect of
preoxidation is rapidly lost and corrosion kinetics will be similar for both

Fig. 7 Gross and net mass changes and cumulated spall after 280 h hot dwell time at 700 °C and a total
of 14 cycles down to room temperature

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preoxidised and ground surface specimens. Severe spallation occurred for the lowest
alloyed steel 1.4982. Noticeable spallation was also seen for 1.4301, while 1.4845
retained most of its oxide. It seems that the corrosion resistance is dependent on the
alloy’s ability to form an oxide that does not crack and spall as well as the capability
to re-form a protective oxide in case of oxide spallation.
In contrast to the exposure at 400 °C, GDOES analyses, Table 5, revealed no
chlorine accumulation within or beneath the oxide. Another difference was that at
700 °C large amounts of condensed metal chlorides were detected in the cooler
parts of the furnace. XRD of these condensed corrosion products gave data which
matched FeCl24H2O, FeCl22H2O and NiCl26H2O. According to [4], FeCl2 is
miscible with CrCl2 and thus solid solution between iron- and chromium chlorides
is expected. Chemical analyses with ICP-MS confirmed that iron was the
dominating element in the evaporated corrosion products, but that a significant
amount of both nickel and chromium was also present.
Metallography of specimens exposed at 700 °C confirms that the lowest alloyed
grade 1.4982 is not suitable for use at this temperature. The alloy suffered from
selective internal oxidation of chromium, as well as formation of an outward
growing iron oxide, Fig. 8(left). The higher alloyed 1.4845 formed a thin
chromium-enriched oxide, without signs of breakaway corrosion, Fig. 8(right).
XRD analysis of the two alloys showed significantly higher amounts of spinel-type
oxide on 1.4982. This type of oxide is regarded poorly protective and is often
associated with rapid inward oxide growth during breakaway corrosion [11, 12].

Discussion

Gas Phase Composition

During combustion of waste and some types of biomass high levels of HCl are
released. According to Nielsen et al [13], the levels when firing biomass range

Table 5 Summary of the corrosion products formed after exposure at 700 °C (280 h)
Material Oxide thickness Maximum Cr/ Chlorine accumulation
(\5% O in GDOES, lm) (Fe ? Cr ? Mn ? Ni) at metal/oxide interface
ratio in the oxide

4982 20 0.37 No
4982, PO at 400 °C 20 0.34 No
4982, PO at 700 °C – – –
4301 – – –
4301, PO at 400 °C 0.5 0.6 No
4301, PO at 700 °C – – –
4845 0.6 0.82 No
4845, PO at 400 °C 0.5 0.8 No
4845, PO at 700 °C 0.5 0.82 No

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Fig. 8 Cross-section of the lowest alloyed EN 1.4982 (a) and surface image of the highest alloyed
1.4845 (b) exposed for 280 h at 700 °C in N2–10O2–5H2O–0.05HCl. 1.4982 shows an outward growing
iron oxide and an inward growing oxide enriched in chromium. Along the grain boundaries a continuous
oxide is present while at the centre of the metal grains a network of unoxidised metal is detected (see
inset). EN 1.4845 does not show any signs of breakaway corrosion and the surface is dominated by
hexagonal Cr2O3 platelets

between 100 and 1000 ppm. During waste incineration even higher levels can be
expected [14, 15]. However, Cl2 rather than HCl is usually considered to be the
corrosive species [3–5]. Research by Abels and Strehblow [16] is often referred to,
showing that an environment comprising Ar–Cl2 is significantly more corrosive than
Ar–HCl. In an HCl-containing environment Cl2 can form according to the Deacon
reaction (Eq. 1).
1
2HClðgÞ þ O2 ðgÞ , Cl2 ðgÞ þ H2 OðgÞ ð1Þ
2
On the other hand, other works [7, 17] have proposed that the formation of Cl2 may
not be a necessary step. Folkeson et al [7] suggested that the corrosion mechanism
can be explained by HCl dissociating at the scale/gas interface according to the
cathodic process:
1
2HClðadsÞ þ O2 ðadsÞ þ 2e , 2Cl þ H2 OðgÞ ð2Þ
2
A corresponding anodic process at the metal/oxide interface creates outward
diffusing cations. The transport of chlorine through the oxide scale would thus be
ionic rather than gaseous.
Thermodynamic calculations using the SSUB3 database in the ThermoCalc R
software [18], Fig. 9(left), shows the equilibrium composition of the present
atmosphere at temperatures between 400 and 700 °C. The Deacon process is a fairly
fast process when catalysed by a metal oxide [19], but the maximum chlorine yield
in such a process decreases with increased temperature [20]. At 400 °C, 7 ppm of
Cl2 is expected and the concentration decreases to 0.7 ppm at 700 °C. Similar
results are obtained from calculations with the HSC v.4.1 database [21]; at 700 °C,
the HSC calculations predict 0.2 ppm of Cl2 compared to 0.7 ppm using the
ThermoCalc software. As evident in Eq. 1 the level of water vapour shifts the

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Fig. 9 Composition of gaseous phases as a function of temperature. In the current exposure with H2O
present (a) almost no Cl2 is expected. If H2O is removed (b), significant Cl2-formation can be expected.
Calculations are made with the SSUB 3 database in the ThermoCalc software

equilibrium reaction and alters the amount of chlorine at equilibrium. While the
amounts of Cl2 formed in an environment comprising H2O–O2–HCl are almost
negligible, the levels are substantially higher in an O2–HCl atmosphere. Evidence of
this behaviour is seen in Fig. 9. It is obvious that chlorine formation requires an
environment rich in oxygen but low in water vapour. In the present study high levels
of HCl rather than Cl2 are expected in the gas phase.

Scale Thermodynamics

Regardless of which chlorine species interacts with the metal, the formation of
metal chlorides is considered central in the corrosion degradation process [1–8]. The
formation and volatilisation of metal chlorides seems to be of particular importance
for the iron-based ferritic and austenitic steels which are widely used in the

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Fig. 10 Equilibrium vapour pressures of solid metal chlorides as a function of temperature. Highest
vapour pressure is expected for the Fe(II) chloride. Calculations are made using the HSC database

Fig. 11 Stability diagram of Fe–25Cr–20Ni (composition similar to EN 1.4845) alloy at 700 °C in an

environment containing Cl2 and O2. The equilibrium environment during the present exposures is in the
region of pure oxides, with a pO2 of 0.1 atm. Calculations are made using the SSUB3 and the TCFE5
databases in the ThermoCalc R software

applications of interest. Considering the equilibrium FeCl2(s) () FeCl2(g) it is

evident that the vapour pressure of FeCl2 is 4 orders of magnitude higher at 700 °C
than at 400 °C, Fig. 10. A similar behaviour is also seen for nickel and chromium
chlorides. The large amount of evaporated metal chlorides observed in this study
after exposure at 700 °C confirms the predictions of increased volatility at elevated
temperatures.
The formation of stable metal chlorides requires a high chlorine activity and a
low oxygen partial pressure, as indicated by the stability diagram in Fig. 11. As a
consequence, chlorides are often confined to the metal/scale interface and are
frequently seen when the corrosion occurs under deposits [17, 22, 23]. In the present

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investigation such interfacial chlorides were seen only in tests at 400 °C and only on
surface ground specimens. In the oxygen-rich environment (10 vol.% O2)
employed, metal oxides are predicted to be the only stable compounds at the gas/
scale interface. Nevertheless, metal chlorides were observed on the surface of the
specimens after exposure at 400 °C and in the cooler parts of the furnace after
exposure at 700 °C. One limitation in the thermodynamic calculation may be that
they include only single metal oxides and chlorides and thus omit mixed phases.
However, a more probable explanation is that chlorides are not readily transformed
to metal oxides even at higher oxygen partial pressure i.e. that the reaction kinetics
are fairly slow. Metal chlorides at the scale/gas interface have also been reported in
several works in the literature [4, 7, 24].

The Role of Temperature and Preoxidation in the Corrosion Process

Exposure at 400 °C showed better performance for the preoxidised specimens and
the characteristic chloride accumulation at the metal/oxide interface was only
observed on specimens with a ground surface. The positive effect of preoxidation is
evident even after 980 h of hot dwell time and a total of 49 thermal cycles down to
room temperature. Furthermore, the behaviour is seen for all investigated alloys,
covering a wide span in oxide composition. The behaviour indicates that the oxides
formed on stainless steels are impermeable to chlorine ingress, unless the scale is
grown in an HCl-containing environment. During such conditions a less protective
scale, comprising a mixture of metal oxides and metal chlorides, will form. It is
likely that such a scale has higher ionic transport rates or even allows for direct gas/
metal contact due to larger defects. During the exposure at 400 °C, no signs of
evaporated metal chlorides were evident, in agreement with the low vapour
pressures expected at this temperature.
At 700 °C the behaviour has changed and no positive effect of preoxidation is
seen. This indicates that the initially formed oxide is degraded and corrosion
resistance is dependent on the ability to reform and maintain a protective oxide
scale. In contrast to the exposure at 400 °C, large amounts of condensed metal
chlorides were detected in the cool parts of the furnace after the exposure at 700 °C.
This is in agreement with the equilibrium vapour pressure of metal chlorides which
predicts significantly higher volatility at higher exposure temperatures. Analyses of
evaporated corrosion products showed that iron, nickel and chromium chlorides had
formed. The fact that large amounts of metal chlorides were detected at cooler parts
of the furnace also indicates that the transformation of metal chlorides into metal
oxides is relatively slow even at high oxygen partial pressures and a temperature of
700 °C.

Corrosion Mechanisms

Chlorine-induced high temperature corrosion is usually described on the basis of

stability of oxides contra chlorides. Modifications of this idea, as well as other
mechanisms have also been proposed. In Fig. 12, a number of published

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Fig. 12 Mechanisms related to the high temperature corrosion of steels in chlorine-containing gas
atmospheres

explanations regarding high temperature corrosion in chlorine containing environ-

ments are summarised:
(i) The chlorine cycle, involving inward diffusion of molecular chlorine,
formation of volatile metal chlorides at the metal/oxide interface and
transformation into metal oxides at the scale/gas interface [4–6, 8].
(ii) Ionic transport of Fe2? and Cl- along oxide grain boundaries [7].
(iii) Interfacial catalysis caused by the accumulation of metal chlorides at the
metal/oxide interface [17]
High temperature corrosion in chlorine-containing environments is clearly a
complex matter and different mechanisms may operate simultaneously. From the
present study it is evident that the corrosion behaviour changes considerably
between the two temperatures and the typical features observed are described
below. At 400 °C it is evident that the surface ground specimens suffer from faster
corrosion compared to the preoxidised specimens. The degradation seems charac-
terised by:
(iv) A chlorine-modified non-protective oxidation process. An oxide grown in a
hostile environment containing HCl will be significantly less protective than
one initially grown in a pure oxidising atmosphere. The detection of
metastable chlorides indicates that both chlorides and oxides could be
expected during the initial corrosion. As exposure continues, new corrosion
products will grow and overtake the initial oxides and chlorides. After longer
exposure times the scale is dominated by oxides, but also chlorides are
present, especially at the metal/chloride interface. This type of scale will be
less protective than one grown in a pure oxidising environment. One reason
may be significantly higher diffusion rates in the chloride-modified scale, in a
similar manner as proposed by [17]. It is evident that the chloride phase is not
confined to the metal/oxide interface and it is also possible that the presence
of HCl affects oxide morphology and defect properties, allowing transport of

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HCl or Cl2 across the scale. At this temperature, metal chloride evaporation
pressures are not sufficient to cause considerable volatilisation.
At 700 °C the behaviour is clearly different with no beneficial effect of
preoxidation. The corrosion is characterised by:
(v) A high degree of direct volatilisation of metal chlorides. This type of
behaviour is frequently observed [1–6, 8] and is in accordance to the well-
known chlorine cycle [5]. However, the metal chloride evaporation is often
associated with a subsequent transformation into metal oxides at higher
oxygen partial pressures. It is difficult to judge to what extent metal chlorides
are directly volatilised and to what extent they are transformed into metal
oxides, but the presence of significant amounts of condensed metal chlorides at
the cooler parts of the furnace indicates that the formation of oxides from
evaporated chlorides is relatively slow. At this temperature there was no
beneficial effect of preoxidation which indicates that the initially formed oxide
is rapidly degraded. The repeated thermal cycling is suggested to reinforce
oxide breakage so that the oxide becomes permeable to both evaporating metal
chlorides and inward diffusing HCl or Cl2.

Conclusions

Three austenitic iron-based alloys (the lower alloyed EN 1.4982, the standard EN
1.4301 and higher alloyed EN 1.4845) were exposed during repeated thermal
cycling in an environment comprising N2-10%O2–5%H2O–0.05%HCl at both
400 °C (980 h) and 700 °C (280 h). The materials were exposed with ground
surfaces and preoxidised for 24 h at 400 or 700 °C.
Equilibrium calculations show that the levels of oxygen and water vapour govern
whether HCl or Cl2 will form. In the present study it seems that HCl rather than Cl2
should be expected. Thermodynamic calculations also show that metal oxides and not
metal chlorides should be stable on the alloy surface. Still, metal chloride formation
is evident at both temperatures. It seems that a kinetically favoured formation of
metastable chlorides has an important role in explaining high temperature corrosion
in oxidising-chlorinating environments, especially at lower temperatures.
A clear positive effect of preoxidation is evident when alloys are exposed at
400 °C. Oxide layers formed during preoxidation effectively suppress chlorine
ingress for all three materials, while chlorine accumulation at the metal/oxide
interface is detected for all specimens with ground surfaces. The result indicates that
chlorine diffusion through a protective oxide is almost negligible. At this low
temperature there is no evidence of metal chloride volatilisation and faster corrosion
rates are explained by increased diffusion rates through a chloride-contaminated
oxide layer rather than by the classic chlorine cycle. The behaviour can be described
as a type of chlorine-modified, non-protective oxidation.
The positive effect of preoxidation is lost at 700 °C. The lower alloyed steels,
1.4301 and particularly 1.4982, form thicker oxides which are more prone to oxide

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cracking. At 700 °C corrosion resistance is only dependent on the alloying level and
the formation of volatile metal chlorides contributes significantly to the material
degradation.

Acknowledgments This work was carried out with a financial support from the Research Fund for Coal
and Steel of the European Community under contract no. RFS-CR-03020. Thanks are expressed to Dan
Jacobsson and David Lindell at Swerea KIMAB for help with XRD-analyses. Magnus Nordling at Swerea
KIMAB is also acknowledged for guidance through calculations with the HSC database.

References

1. N. S. Jacobson, Oxidation of Metals 26, 157 (1986).

2. Y. Y. Lee and M. J. McNallan, Metallurgical Transactions A 18A, 1099 (1987).
3. F. H. Stott and C. Y. Shih, Materials and Corrosion 51, 277 (2000).
4. A. Zahs, M. Spiegel, and H. J. Grabke, Corrosion Science 42, 1093 (2000).
5. H. Asteman and M. Spiegel, Corrosion Science 49, 3626 (2007).
6. A. Zahs, M. Spiegel, and H. J. Grabke, Materials and Corrosion 50, 561 (1999).
7. N. Folkesson, L. G. Johansson, and J. E. Svensson, Journal of Electrochemical Society 154, 515
(2007).
8. S. Chevalier, S. Ched’homme, A. Bekaddour, K. Amilain-Basset, and L. Buisson, Materials and
Corrosion 58, 353 (2007).
9. P. Kofstad, High Temperature Corrosion, Chap. 11, (Elsevier Applied Science, London, 1988).
10. A. L. Marasco and D. Young, Oxidation of Metals 36, 157 (1991).
11. F. Liu, J. E. Tang, T. Jonsson, S. Canovic, K. Segerdahl, J. E. Svensson, and M. Halvarsson,
Oxidation of Metals 66, 295 (2006).
12. F. Liu, J. E. Tang, H. Asteman, J.-E. Svensson, L.-G. Johansson, and M. Halvarsson, Oxidation of
Metals 71, 77 (2009).
13. H. P. Nielsen, F. J. Frandsen, K. Dam-Johansen, and L. L. Baxter, Progress in Energy and Com-
bustion Science 26, 283 (2000).
14. P. Steinmetz and C. Rapin, Materials Science Forum 251–254, 505 (1997).
15. G. Y. Lai, High-Temperature Corrosion and Materials Application, Chap. 12, (ASM International,
Materials Park, Ohio, 2007).
16. J.-M. Abels and H.-H. Strehblow, Corrosion Science 39, 115 (1997).
17. P. Szakalos, P. Henderson, and R. Pettersson, Proceedings of the 16th International Corrosion
Conference, (Beijing, China, 2005).
18. B. Sundman, B. Jansson, and J.-O. Andersson, Calphad 9, 153 (1985).
19. U. Nieken and O. Watzenburger, Chemical Engineering Science 54, 2619 (1999).
20. B. K. Gullet, Chemosphere 20, 1945 (1990).
21. HSC Chemistry for windows v 4.1, Outokumpu Research Oy, software and database
22. R. Pettersson, J. Flyg, and P. Viklund, Corrosion Engineering, Science and Technology 43, 123
(2008).
23. P. Viklund, R. Pettersson, A. Hjörnhede, P. Henderson, and P. Sjövall, Proceedings Eurocorr, The
European Corrosion Congress, Paper no. 1289 (Edinburg, UK, 2008)
24. E. Reese, E. M. Muller-Lorenz, and H. J. Grabke, Journal de Physique 3, 133 (1993).

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