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P R E P R I N T – ICPWS XV

Berlin, September 8–11, 2008

Corrosion of steels in H2O-CO2 atmospheres at temperatures between


500°C and 700°C

D. Huenert, W. Schulz and A. Kranzmann

Federal Institute of Materials Research and Testing


Unter den Eichen 87, 12205 Berlin, Germany

Email: daniela.huenert@bam.de,
wencke.schulz@bam.de,
axel.kranzmann@bam.de

The introduction of carbon capture technology into thermal power plants benefits from combustion of fuel and
pure oxygen due to high partial pressures of CO2 in the flue gas. Consequently IGCC plants with 80 bar
reactors and high temperature turbine equipment, boilers with 700°C superheater tubes will be the next
generation power plants. In this paper, the attack of a model gas composition on different typical power plant
construction steels with chromium contents in the range of 1 to 24% is discussed. The test conditions were an
corrosion time up to 1000 h, a pressure of 80 bar, a fast flowing gas and temperatures between 500 and 700°C
depending on the maximum working temperature of the individual steel. In particular, the growth of FeO at
temperatures lower than 570°C, which is the eutectic decomposition temperature in the oxygen-iron phase
diagram, is observed. Iron carbides are primarily formed in low alloyed steels near the oxide steel interface.
For the studied steels containing more then 9% chromium, a growth of Fe3O4 and Fe-Cr-spinel was typical.
Steels with chromium contents below 12% did not form a dense and therefore protective Cr2O3 layer. The
oxide scale thickness increases strongly with temperature and decreases with raising chromium content. Data
of oxide scale thickness up to corrosion time of 1000 h will be presented. In the test environment the
maximum working temperature was estimated to be 50K below the working temperatures in current power
plant environments.

Introduction In the Oxyfuel power plants, pure oxygen will


be inserted for the combustion, resulting in a flue
The discussion about the effect of rising CO2 gas composed of H2O and CO2. In addition with the
concentration in air had caused, that all industrial unconsumed oxygen and fuel specific impurities,
nations search for options to decrease the part of these gases compose the flue gas.
CO2 in the atmosphere. The expression of this The metallic units have to resist surface
collective aim is the Kyoto protocol, in which the temperatures of 950°C in gas turbines and 650°C in
involving states are committed to reduce the part of coal burning power plants. Future power plants are
CO2, CH4, N2O, H-FKW/HCF, FKW/PFC and SF6 supposed to work in the range of 700°C. Less is
to an amount of 5% in a time period from 1990 to known about the oxidation resistance of
2012. If all states fulfil their obligations, the part of conventional steels in advanced power plants
CO2 in the air could be stabilized below 350 ppm. during service under future power plant conditions.
Industrial facilities and power plants are well The research work of the BAM is focused on the
localised emission sources and produce corrosion behaviour of power plant steels and
approximately one fourth of the emitted CO2. The nickel based alloys with different chromium
running research programs of the Federal Ministry contents in contact with combustion gases
of Economics to develop CO2 Reduction consisting of H2O, CO2 and O2 [1] [2]. The
Technology (COORETEC), as well as EU- oxidation behaviour, oxidation rates and the formed
programs, consider the complete process from CO2 oxide scales with its phase composition of one low
accruement to CO2 suspension. Consequently the alloyed steel, three 9-12% Cr-steels and one
application of power plants with CO2 separation is austenitic steel in H2O-CO2 has been the subject of
an aim. The technologies with CO2 capture require our study.
rising efficiencies, which cause higher working
temperatures, pressures and modified gas
compositions. In this account better knowledge Experimental
about the corrosion behaviour of the materials have
to be obtained. In the experiments commercial available steam
generation tubes were used as tubular samples,
which were streamed by pressurised combustion
gases from the inside. At the outside laboratory air
at ambient pressure was provided and caused an
oxidation. The flowing combustion gas consisted of
H2O and CO2 (30 mol %, 70 mol %) at a pressure
of 80 bar according to the main combustions
products in IGCC and Oxyfuel. Impurities were left
out to study the corrosion mechanisms of the major
components. Figure 2: Sample for analyses
A thermal load was applied by heating the tubes
from the outside, allowing the experimental study
of different temperatures in one tube. The tubes Measurement of scale thickness
were exposed at temperatures between 500°C and On each sample (fig. 2), 100 single measuring
700°C for a period of 250 h and 1000 h. The gas points on eight different positions were measured
velocities varied with rising inner tube diameter around the tube segment to give a good accuracy of
between 2,1 and 0,1 cm/s. At the end of the tubes, a scale thicknesses and to evaluate irregularities on
gaseous or fluid sample can be removed from the the cross section.
flue gas to clarify, which alloying additions
evaporate during the corrosion process.
The exact compositions of the investigated steels Results
are shown in table 1. The ferritic and martensitic
materials differ mainly in chromium content. As a Microstructure of the base material
substitute of the low alloyed steels, 13CrMo44 (1% The low alloyed steel 13CrMo44 has a ferritic
Cr), as high alloyed steels, the P92, X20 and an microstructure. A martensitic microstructure is
experimental steel B (9-12% Cr) and as austenitic characteristic for the steels X20CrMoV12-1, B and
steel, the DMV 310 N was investigated. P92. As an example of austenitic steel, DMV 310 N
containing 24% chromium was used.

Composition of oxide scales


In a flowing mixture of H2O-CO2 at a pressure
of 80 bar in a temperature range between 550°C
and 700°C, differences in phase compositions were
observed after an exposure time of 1000 h [fig. 3].

Figure 1: Sketch of facility for the corrosion at 80


bar

Table 1: Composition of the testing basic material

Figure 3: General phase sequence of steels


differing in chromium content
Preparation
After the corrosion tests, tubes were prepared A typical phase sequence of a low alloyed steel
with a fixation spray first and subsequently filled at 600°C is shown in fig. 4a. Above the wustite
with epoxy resin in order to prevent a spalling off point a heterogeneous layer in contact with the base
of the oxide scales during machining. Exact material has been formed consisting of 50% FeO
information was published elsewhere [3]. The and 50% iron carbides. The carbides are arranged
oxidation products were analysed with optical like columns in a wustite matrix. According to
microscopy, scanning electron microscopy rising oxygen partial pressures from the metal-
(SEM/EDX, LEO 1520 VP, JEOL microprobe oxide interface to the oxide-gas interface, the
JXA-8900 RL) and transmission electron following phases consist of wustite and maghemit.
microscopy (JEOL 4000). Maghemit is a defect spinel with the structure of
magnetite but the overall formula of hematite [5].
Maghemit is a result of cooling, in which the iron
mobility is decreased and oxygen diffusivity is

2
increased [4]. Below the wustite point the scale
consists of an inner magnetite and an outer
hematite layer according to the thermodynamically
preferred phases below the wustite point. The
heterogeneous mixture of wustite and iron carbides
observable at higher temperatures is absent at Fe3O4
550°C.

Fe2O3 Fe3O4 + Spinel

FeO
chromium precipitates
FeO + Fe3C
Alloy (P92)
Alloy (13CrMo44)
c)
a)

On 9-12% Cr-steels, a continuous and


multilayered oxide scale has been formed. Figure
4b and c shows chromium precipitates in an inner
FeO matrix, followed by Fe3O4 with spinel stringers
and an outer thin layer of Fe2O3 (maghemit) at the
oxide-gas interface.

Fe2O3

d)

Fe3O4 + spinel stringers

iron oxide
Alloy (B) Cr2O3
b)

In the case of alloy B, the maghemit phase is


absent. Carbides are only found in the case of Co
and W free alloys at the metal-oxide interface.
Despite of the similar chromium content of steel Alloy (DMV 310N)
X20 and B, the structure of their oxide scales is
different. During the corrosion of X20, oxide e.)
islands as well as areas with thin oxides were
formed (fig. 4d). In contrast to the islands with in Figure 4: Oxide scales of a) 13CrMo44 b) steel B
this manner described phase sequence, the thin c) P92 d) X20CrMoV12-1 and e)
neighbouring oxide scale shows only iron rich DMV310N in flowing H2O-CO2 at a
oxides with no chromium spinel. This oxide pressure of 80 bar at the maximum
morphology is well known for 9-12% chromium working temperatures of the individual
steels exposed to air at high temperatures [6]. A steels after an exposure time of 1000 h
continuous oxide scale with no islands has been The microstructure of the oxide scale on an
austenitic steel at 730°C is shown in fig. 4e. A thin
formed on the steel B.
and continuous chromium oxide layer was formed

3
in contact with the base material, which is followed
by an iron oxide (Fe2O3). 18
500

relative scale thickness, µm


xscale
xrel = 550

Scale thicknesses 13
50µm 600

Depending on the temperature, different oxide 650

scale thicknesses for the investigated steels were 8

observed. Figure 5 shows the scale thicknesses as a


function of temperature after an exposure time of 3

1000 h. Generally, the oxide scales of 13CrMo44,


P92 and alloy B becomes thicker with increasing -2
0 5 10 15 20 25
temperature. A non-arrhenius-typ scale growth is Chromiumequivalent

ascertained for the steel X20CrMoV12-1


potentially indicating changes in reaction Figure 6: Relative scale thickness versus
mechanism. The oxide scale increases with chromium equivalent at different
temperature until a temperature of 600°C is reached temperatures
and is reduced for higher temperatures.
At the austenitic steel (DMV310N) with the
10000 highest chromium content of 24 %, thin scales of
13CrMo44
P92 approximately 5µm has been grown at all
1000
X20CrMoV12-1
investigated temperatures.
scale thickness, µm

B
DMV 310 N Figure 6 shows the relative scale thickness data of
100
the studied steels (table 1) during the exposure in
flowing H2O-CO2 (30-70 mol %) at 80 bar as a
function of chromium equivalent and different
10
temperatures. The scale thicknesses are given
relative to the scale thickness of alloy B at 500°C
1
9,8 10,8 11,8 12,8
over 1000 h at 80 bar in order to compare the scale
-4
1/ T *10 [1/K] thicknesses. A scale thickness of 50 µm was found
in this case. The dashed lines illustrate the assumed
Figure 5: Logarithmic exposition of oxide scale dependence on chromium equivalent. The
thickness data for the investigated steels temperature effect on scale thickness is pronounced
after an 1000 h exposure in a flowing for low alloyed steels and marginal for steels with
mixture of H2O-CO2 at a pressure of 80 higher alloying additions. With rising temperatures,
bar and at different temperatures the curve maximum has been shifted to higher
values of the relative scale thickness. The reduction
At the steel 13CrMo44 with the lowest of oxide scale thickness is not only due to an
chromium content, thick oxide scales has been increased level of chromium in the alloy.
developed during the corrosion in a flowing and Especially secondary alloying additions like
pressure loaded mixture of H2O and CO2. This tungsten and cobalt seem to influence the corrosion
ferritic steel shows the highest scale thicknesses behaviour significantly and lower the relative oxide
with rising temperature compared to steels higher scales. The relative scale thickness is also
in chromium content. After a temperature of 550°C dependent on pressure of the gas mixture. With
a sharp increase in scale thickness is observable. increasing pressure the oxide scale becomes thicker
The high alloyed steels P92, alloy B and X20 [4].
present a relatively low scale thickness below Figure 7 shows the scale thickness of the
600°C (fig. 5). Above 600°C an increased oxide studied steels differing mainly in chromium content
scale growth for the steels P92 and steel B is during the exposure in H2O-CO2 (30-70 mols %) as
observable. In contrast, the steel X20 shows a a function of time at temperatures of 500, 550 and
reduction of scale thickness with rising 600°C. For the low Cr-steel 13CrMo44 an
temperatures above 600°C. Scale thickness incubation time for the exposure at a pressure of 80
reducing factors could be spallation, preparation bar is characteristic at all investigated temperatures.
effects, fast evaporation of alloying elements from At the beginning of oxidation, the scales do not
the oxide surface [7] or a change in corrosion grow very much, whereas after an exposure of 1000
mechanism. h substantially thicker scales are formed. Already,
small additions of chromium show a substantially
decreasing effect on scale thickness. These 9-12%
chromium steels grow probably parabolic. The
austenitic steel DMV 310N shows the thinnest
oxide scale of 5 µm after a 1000 h corrosion time.

4
thermodynamically preferred phase and below
570°C magnetite is the stable phase. Magnetite
exhibits a spinel structure with limited defects,
resulting in the reduction of oxide scale growth. In
our experiments the wustite was observable below
the wustite point. Alloying additions like Mn have
the ability to reduce the wustite point temperature
[14]. The low alloyed steel 13CrMo44 has
sufficiently high amounts of Mn, which could
500°C result in the stabilisation of wustite below 570°C
and cause the high oxide scale growth down to low
temperatures. Another explanation for existence of
wustite below 570°C is that the equilibrium is not
reached due to the fast diffusion and reaction of
iron to form oxides. An additional explanation for
550°C the temperature of 600°C considers the formation
of a laminar grain boundary layer at test conditions,
where oxygen is provided depending on the oxygen
diffusion through the boundary layer. The deep
decreasing partial pressure profile in the laminar
media layer could meet the FeO/Fe3O4-equlilibrium
oxygen partial pressure and hence favour the
formation of wustite.
An addition of chromium leads to a significant
decrease in oxidation rates because of the formation
of protecting Fe-Cr-spinels [4] [6]. Depending on
chromium content, Fe-Cr-particles or a continuous
and protecting layer of Fe-Cr-spinel has been
600°C formed at the martensitic 9-12% chromium steels.
The spinel is located in the inner corrosion zone
and show zones enriched in chromium depending
on the chromium content in the alloy. At the alloy
interface a chromium rich spinel, and close to the
gas side, an iron-rich spinel is exclusive observed.
According to the reported results, a dense Cr2O3-
layer could not be observed for any of the
examined 9-12% Cr-steels after a 1000h exposure
in flowing H2O-CO2 at different temperatures
(relevant for power plants). It is reported that in
Figure 7: Scale thickness as a function of pure steam, a thin protecting Cr2O3-layer is first
time at temperatures of 500, formed above a chromium content of 15%, which is
550 and 600°C. not stable due to interdiffusion by iron and
formation of iron rich oxides [6] [8] [9]. The
observed results in H2O-CO2 indicate that H2O has
Discussion a more lasting effect on the phase sequence for the
high chromium steels as CO2 has. The analysed
The corrosion mechanisms and observed oxide iron-rich spinel cause a loss of protective properties
scale compositions in a flowing H2O-CO2- of the oxide scale [10] [11] [12] [13]. At the steels
atmosphere at different temperatures are changed close to the gas side, maghemit was observable for
compared to the corrosion results in pure H2O, CO2 all investigated steels with the exception of alloy B.
and O2 respectively. During corrosion and during cooling a deep oxygen
Under the described conditions the stable oxide profile from the metal surface to the oxide/gas
phase on the low alloyed chromium steel interface is formed. Accordingly, the iron vacancies
13CrMo44 is wustite, despite the oxygen partial are growing in oxygen rich sections, near the
pressures in the mixture clearly favour the oxide/gas interface. In the same direction the
formation of hematite at every examined oxygen rich wustite becomes metastable below
temperatures. Because of its defect rich structure, temperatures of 570°C and decomposes in
wustite leads to a fast diffusion of iron to the magnetite and residual wustite [14]. Residual
outside and the enhanced growing of oxide scales. wustite was also observed near the gas/oxide
Above the wustite point in the Fe-O binary phase interface in our experiments for the steel
diagram at 570°C, wustite is the 13CrMo44, supporting this theoretical mechanism.
The decomposed magnetite could further transform

5
into maghemit, because of the high oxygen supply The authors acknowledge the financial support
at the oxide/gas interface [4]. from the Ministry of Economics, Germany (Grant
In contrast to the 9-12% chromium steels, the ID: 0327727B) and the COORETEC program.
austenitic steel with the highest chromium content
of 24% shows a dense and continuous Cr2O3 layer
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