130 Sulfur Dioxide

After preoxidation at 1,073 K (800
C) for 1 min in a stream of air (70 cm/min)
with a moisture content of 600 ppm, the weight increase of a steel with 10 % Cr was
still only 0.3 mg/cm2 after a period of 140 hours. By addition of B2O3, a weight
increase of 0.5 mg/cm2 was determined after a period of 106 hours. The thickness
of the protective oxide film was 2 to 3 lm in the first case and 4 to 5 lm with the
added B2O3. After a treatment time of 10 min in air under the above-mentioned pre-
oxidation conditions, the weight increase in an argon atmosphere containing 10 %
SO2 was still only 0.2 mg/cm2 after a period of 240 hours [264].

– Areas of application –
Studies on the fatigue strength in “sulfurous acid” of the steel type 403 (X6Cr13) at
room temperature have shown that no influence on the growth of fatigue cracking
was detectable at pH values above 3. In contrast, the crack growth rate increased by
a factor of more than 2 at a pH of 2 and may be influenced by both pH and tempera-
ture.
Cracking in “sulfurous acid” in the pH range 2.5 to 3 proceeds faster at 366 K
(93
C) than at 296 K (23
C).
At 366 K (93
C), the rate of crack growth is up to 3 times faster than at 296 K
(23
C) [266]. The steel investigated had the following chemical composition:
Fe-0.10C-0.44Mn-0.016P-0.028S-0.26Si-12.49Cr-0.25Ni-0.45Mo-0.08Cu.
According to DIN EN 10088-3, this steel can have a minimum chromium content
of 12 %, and is, therefore, also mentioned in Section A 17. Turbine blades are made
from it.
Chromium steel with 7 % chromium is used as the material for an SO2 cooler in
a sulfuric acid plant. The maximum gas temperature is 1,173 K (900
C) on the pri-
mary side and 523 K (250
C) on the secondary side. The cooling capacity is quoted
as 1.74  107 kJ/h [267].

A 18 Ferritic chromium steels with more than 12 % chromium

A 19 Ferritic-austenitic steels with more than 12 % chromium

These steels generally have a better corrosion resistance than the steels with up to
12 % chromium. Like most metals, they are not attacked by dry, gaseous SO2 or
anhydrous, liquid SO2.
Chromium steels with 17 % Cr and molybdenum are attacked by dry SO2 at 673 K
(400
C) at a rate of less than 0.11 mm/a (4.33 mpy); they can be used for chimney
components.
These steels also have a maximum corrosion rate of 0.11 mm/a (4.33 mpy) at
room temperature up to 408 K (135
C) under 0.4 MPa in saturated aqueous solu-
tions of sulfur dioxide. However, the corrosion rate under 0.8 MPa can rise to
1.1 mm/a (43.3 mpy). The molybdenum-free 17 % chromium steel is not resistant
in aqueous SO2 solution even at room temperature (11 mm/a (433 mpy)). In the
cooking acids of the cellulose and paper industry (for example in an acid of pH 1.3
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 A 18 Ferritic chromium steels with more than 12 % chromium / 131
A 19 Ferritic-austenitic steels with more than 12 % chromium

containing 4 % SO2 and 1 % CaO, or 8.2 % SO2 in total, of which 7 % is free SO2),
the molybdenum-containing 17 % chromium steel has a corrosion rate at room tem-
perature of less than 0.13 mm/a (5.12 mpy). At 373 K (100
C), the corrosion rate
rises to up to 11 mm/a (433 mpy). The molybdenum-free steels are also no longer
usable under these conditions at room temperature [39].

– Atmospheric corrosion –
Passive oxide layers form on chromium steels at or above Cr contents of 12 %, offer-
ing good protection from uniform general corrosion. At a content of at least 12 %,
chromium can transfer its natural passivity in combination with iron to the latter,
which means that iron also becomes passive. However, like all passive, stainless
steels, they exhibit a certain susceptibility to local attack, such as pitting corrosion
and crevice corrosion. The formation of aeration cells if electrolytic corrosion is pos-
sible in the presence of sulfur dioxide is important for the resistance of these steels
to the atmosphere. This electrolytic corrosion is triggered off by the presence of a
film of liquid on the surface, including drops of condensate.
As already mentioned, the conditions in an atmosphere containing sulfur dioxide
can be imitated in the Kesternich test according to DIN 50018 with the addition of
sulfur dioxide.
Molybdenum-free chromium steels with 17 % Cr are attacked locally, red-brown
corrosion products being formed. Molybdenum-free chromium steels with about
17 % chromium and molybdenum-free, austenitic chromium-nickel steels with
about 18 % chromium differ here only in the severity of the attack, but not in their
fundamental resistance [268].
After removal of the corrosion products, pitting corrosion, which may extend
deep into the material, is detectable on the surface. In contrast to the action of chlo-
rides, the holes formed by aeration cells are usually irregular in shape, a feature
detectable by metallography [268]. Molybdenum-containing, ferritic chromium
steels with 17 % Cr and more than 1 % Mo and austenitic chromium-nickel steels
are not attacked during testing by the Kesternich test. The addition of molybdenum
decreases the rate of corrosion in the active state and hence increases the capacity
for passivation of the steels. In an industrial atmosphere in outdoor weather condi-
tions, other atmospheric pollutants and deposits, as well as sulfur dioxide and dust,
should be taken into account (see also the Introduction).
The corrosive attack is intensified by pollutants which adhere to the surface. Spec-
imens subjected to cleaning were attacked less than those which were not cleaned.
The side of the specimens exposed to the weather had a poorer surface appearance
due to soot deposits.
The corrosion behavior of these materials is influenced by the state of the surface.
Specimens ground with 180 grain were rusted more heavily than cold-rolled, heat-
treated and pickled specimens, regardless of the amount of cleaning (cleaned or not
cleaned) and weather exposure.
Corrosion studies over a period of 10 years have shown that the ferritic 17 % chro-
mium steel X8Cr18 (1.4015, UNS S43080) is attacked severely in industrial and sea
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132 Sulfur Dioxide

air. Pitting to a depth of 50 lm develops on the surface. This is probably a conse-

quence of aeration cells in industrial air due to the action of sulfur dioxide, and chlo-
ride corrosion in sea air [268].
Corrosion studies in the test climate according to the Kesternich test confirm the
studies on the molybdenum-free chromium steels in [268]. After the first round of
tests, the steels X12Cr13 (1.4006), X8Cr18 (1.4015) and X3CrTi17 (1.4510) showed
heavy rusting. In contrast, the molybdenum-containing steel X3CrTi17 containing
1.72 % Mo was not attacked. This corrosion pattern also did not change fundamen-
tally up to the 5th round of tests, except that the rusting on the surface of the molyb-
denum-free grades increased [269].
Corrosion studies on the steel 430 (X6Cr17, 1.4016) in a damp atmosphere (rel.
humidity > 88 %) have shown that the corrosive attack on the steel increases as the
SO2 content increases.
Hardly any corrosive attack is recorded in an SO2-free medium. Dusts of about
0.1 mg/cm2 containing Al2O3, carbon, (NH4)2SO4 and FeSO4 on the surface of the
specimens caused no pitting corrosion. The highest material consumption was
caused by carbon deposits and was 10 mg/dm2 after 4 months. Pitting corrosion
occurred only in the presence of NaCl (0.1 mg/cm2) with a maximum depth of
attack of 40 lm after 4 months. The surfaces of the specimens were still acceptable
under these conditions. At an SO2 content of 100 ppm, the specimens showed
severe corrosion phenomena on the surface. They had become visually unusable
due to the chloride content. The material consumption per unit area after 4 months
was 66 mg/cm2, and the maximum pitting depth 160 lm. Further details can be
found in Table 51. At an SO2 content of 3,000 ppm, the maximum pitting depth due
to NaCl contamination rises to 0.3 mm; this is further exceeded by Al2O3 and
(NH4)2SO4 on the surface.
Long-term studies on this chromium steel over 12 years in the atmosphere of
London led to the results in Table 52.
In the context of SO2 pollution in the London air, see also Tables 8 and 9 and
Section A 20. Table 52 shows that the industrial atmosphere in Stratford is not as
corrosive as that in Shoreham close to the sea. In Stratford, the pitting density on
the steel specimens was determined as 131 pits per mm2, and was greater than in
the mixed atmosphere of Shoreham (105/mm2). The maximum depth of pitting on
the specimens was significantly lower in Stratford, at 7 lm, than in Shoreham, at
33 lm. Molybdenum-free chromium-nickel steels are less suitable than chromium
steels under these conditions.
The chromium steel 18Cr-2Mo-Ti containing 2.27 % Mo shows a very good corro-
sion behavior in a marine atmosphere (Malm). After an exposure time of 5 years,
no noticeable areas of attack were found on the surface of the steel either in the
pickled, ground or polished state. The steel also showed the same good corrosion
resistance in an urban atmosphere (Stockholm). Since a marine climate is more cor-
rosive than an industrial climate, this molybdenum-containing steel can be used in
comparable atmospheres.
The depth of attack (local corrosion) on this chromium steel by chlorides in a
marine atmosphere was 0.05 mm after 5 years [270].
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 A 19 Ferritic-austenitic steels with more than 12 % chromium 133

Electrochemical studies for evaluation of the corrosion resistance of microcracked

chromium layers as corrosion protection on steel and of the steels X6CrMo17-1
(1.4113, AISI 434 ) in dilute sulfuric acid and 3 % sodium chloride solution have
shown that the chromium steel is more resistant than the chromium layers in dilute
sulfuric acid and, therefore, has a better corrosion behavior in an industrial atmo-
sphere. The studies revealed no signs of pitting corrosion on this steel [273].

– Corrosion in aqueous, SO2-containing solutions –

Chromium steels are not suitable for use in “sulfurous acid” [39, 41].
The steel X4CrNiMo16-5-1 (1.4418), which can be subjected to martensite harden-
ing and tempering, is practically free from attack in “sulfurous acid” (1.5 %) at tem-
peratures up to 323 K (50
C). The material consumption rate is quoted as 0.001 g/m2 h
(0.001 mm/a). The same source quotes the material consumption rate of the steel
X17CrNi16-2 (1.4057, AISI 431) under these conditions as 2.0 g/m2 h (2.2 mm/a)
[271]. To obtain a good corrosion resistance of the steel X4CrNiMo16-5-1 to intercrys-
talline corrosion, the heat treatment must meet the requirements shown in Figure
75. This graph shows heat treatment regions which must be avoided in order to
obtain a high resistance to intercrystalline corrosion.

Figure 75: Sensitization diagram of the steel X4CrNiMo16-5-1 (1.4418) during testing by the
Strauss test according to DIN EN ISO 3651-2 for susceptibility to intercrystalline corrosion. Treat-
ment: 1,223 to 1,273 K (950 to 1,000
C)/oil + tempering [271]

During testing by the Strauss test, prescribed samples remain in a boiling test
solution of water, sulfuric acid and copper sulfate containing electrolytic copper fil-
ings for 15 hours [271].
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134 Sulfur Dioxide

A chromium steel containing 26 % Cr and 1 % Mo also has a very good resistance

in “sulfurous acid”. The corrosion rates in 1 % and 9 % acid at 353 K (80
C) are
quoted as 0.01 mm/a (0.39 mpy). In contrast to this, the molybdenum-alloyed chro-
mium-nickel steel 316 L (X2CrNiMo17-12-2, 1.4404) shows a corrosion rate of
8.13 mm/a (320 mpy) in 1 % “sulfurous acid” and 2.8 mm/a (110 mpy) in 9 % acid
at the same temperature [272].
The recently developed ferritic chromium steels with low carbon and nitrogen
contents show a good resistance to intercrystalline corrosion.
According to [272], the chromium steel mentioned (26Cr-1Mo) has a low sensitiv-
ity to intercrystalline corrosion. The better corrosion resistance of the 26Cr-1Mo
steel (E-Brite 26-1 , UNS S44627) in gas washing solutions compared with 316 L
(X2CrNiMo17-12-2, 1.4404) is confirmed in [274]. If chlorides are present, as may
occur in gas washing plants, the steel C-Brite 29-4 containing 29 % Cr and 4 % Mo
is recommended.
This has a better resistance to pitting corrosion than the steel with a lower chro-
mium and molybdenum content [274].
A resistance of chromium steels to pitting corrosion which is adequate in practice
is achieved at chromium contents greater than 25 %. These steels, with extremely
low nitrogen and carbon contents, are called ”superferrites” [284].
The corrosion rate of 17 % chromium steels without molybdenum in SO2-contain-
ing solutions found in the food industry is low. It is only 5  10–4 to 2.5  10–3 mm/a
(0.02 to 0.10 mpy) at a maximum of 0.08 % SO2, but 2.2  10–3 to 0.77 mm/a (0.09
to 30.3 mpy) in vegetable water containing 0.11–0.12 % SO2 [275]. By testing of
molybdenum-free 17 % chromium steels in the Kesternich test, the passivity of the
steels is eliminated and they become corroded [276], as already reported in [269].
The chromium-molybdenum steel (21Cr-3Mo-Ti) showed the best corrosion be-
havior in an SO2 washing solution containing 2,000 mg/l NaHSO3 and 3,000 or
30,000 mg/l Cl–, due to addition of NaCl, at a pH of 5.3, established with NaOH,
and a test temperature of 363 K (90
C). The maximum corrosion rates (test duration
1 week) were 0.09 mm/a (3.54 mpy) in the solution containing 3,000 mg/l chloride,
and 0.2 mm/a (7.87 mpy) in a solution containing 30,000 mg/l chloride. The steel is
more resistant than chromium-nickel steels of the type 316 and 304 under these
conditions. The corrosion data are summarized in Table 42 [277]. Table 43 contains
the chemical composition of the steels.
The molybdenum content is very important for the corrosion resistance in SO2
washing solutions, as can be seen from the corrosion rates of the chromium steels,
particularly the chromium-nickel steels. Chromium-nickel steels with low molybde-
num content are the least resistant under these conditions and far inferior to the
molybdenum-containing chromium steels (Table 42).
Studies on the fatigue strength of steel specimens of the type 403 in “sulfurous
acid” at pH values above 3 showed no influence on the growth of fatigue cracks at
room temperature. At pH 2 and room temperature, the rate of fatigue cracking rose
by a factor of 2 and the corrosion increased. The crack growth in “sulfurous acid”
proceeds up to 3 times faster at 366 K (93
C) than at 296 K (23
C) (see also Section
A 17) [266].
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 A 19 Ferritic-austenitic steels with more than 12 % chromium 135

Material* Mo Corrosion rate, mm/a (mpy)

addition %
3,000 mg/l Cl– 30,000 mg/l Cl–

Sample 1 Sample 2 Sample 1 Sample 2

AISI 304 0.22 75.4 (2,969) 96.1 (3,783) – –

AISI 316 2.3 16.6 (654) 11.0 (433) 81.0 (3,190) 1.8 (70.9)

AISI 316 2.9 0.14 (5.51) 0.14 (5.51) 0.2 (7.87) 0.4 (15.7)

Fe-22Cr13Ni5Mn 2.1 5.3 (209) 0.1 (3.94) 0.5 (19.7) 0.6 (23.6)

Fe-18Cr2MoTi 2.0 0.83 (32.7) 0.7 (27.6) 1.8 (70.9) 2.0 (78.7)

Fe-21Cr3MoTi 3.0 0.05 (1.97) 0.09 (3.54) 0 (0) 0.2 (7.87)

(laboratory specimen)

E-Brite 26–1 1.2 0.09 (3.54) 0.2 (7.87) 1.8 (70.9) 2.0 (78.7)

* see Table 43

Table 42: Corrosion rates of stainless steels in SO2 washing solutions containing 2,000 mg/l
NaHSO3 and 3,000 or 30,000 mg/l Cl– (in the form of NaCl), pH 5.3, saturated with O2 at 363 K
(90
C) [277]

The chromium steel 430 (1.4016, X6Cr17) is very severely attacked in spring
water at 371 K (98
C) and pH 2.2 with a content of 53 ppm Cl–, 255 ppm SO42–,
3 ppm K+, 7.5 ppm Na+ and 52 ppm Fe2+ ions. The corrosion rate after a test dura-
tion of 46 h is quoted as 93 mm/a (3,661 mpy). The steel cannot be used under
these conditions (see Table 55).

Material Chemical composition, %

C Mn Si S P Cr Ni Mo N Cu Ti Nb V
AISI 304 0.063 1.72 0.43 0.013 0.026 18.55 10.48 0.22 0.027
AISI 316 0.060 1.50 0.67 0.010 0.015 17.32 13.12 2.28 0.037
AISI 316 0.059 1.20 0.32 0.011 0.019 17.20 13.27 2.89 0.027
Fe-22Cr13Ni5Mn 0.050 5.44 0.42 0.010 0.015 21.48 12.36 2.12 0.27 0.16 0.19 0.20
Fe-18Cr2MoTi 0.009 0.40 0.37 0.007 0.008 18.95 < 0.01 2.00 0.01 < 0.01 0.17
Fe-21Cr3MoTi 0.015 21.48 3.03 0.016 0.36
(Climax)
E-Brite 26-1 0.0020 0.01 0.25 0.010 0.011 26.19 0.09 1.17 0.010 0.02

Table 43: Chemical analysis of the steels from Table 42 (bal. Fe) [277]

The chromium steel X6Cr17 is attacked hardly at all in steam at 420 K (147
C)
with a flow rate of 30 m/s under a pressure of 0.42 MPa. The steam consists of 97.9
H2O and 2.1 gas (percent by volume). The gas composition is as follows (percent by

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136 Sulfur Dioxide

volume): 51.4 CO2, 44.2 H2S, 2.0 SO2 and a balance of 2.4. The pH of the conden-
sates is 6.5 (Table 56).
The corrosion loss after a test duration of 1,030 h is about 1 lm/a (0.04 mpy)
[247]. Chromium-nickel steels are even more resistant under these conditions.
The corrosion of this steel (X6Cr17) by volcanic gases is more severe. The vapors
consist of (percent by volume) 98.2 H2O and 1.8 gas of the following composition:
71.4 CO2, 22.3 H2S, 2.9 SO2 and a balance of 3.4. The temperature is not stated.
After a test duration of 1,769 h, the corrosion rate is 0.02 mm/a (0.79 mpy)
(Table 54).
In the gas purification in sulfuric acid production plants, gases are cooled from
313–318 K (40–45
C) to 303 K (30
C) by spraying. The aqueous solution of the ab-
sorber at the intake contains 0.5–0.7 % SO2, 41–48 % CaO, 13–35 % CaSO3 and
9–19 % CaSO4 at a pH of 5–11. The solution at the outlet contains 0.01–0.14 % SO2,
40–45 % CaO, 7–35 % CaSO3 and 9–25 % CaSO4 at pH 4–6.
The corrosion rate on the chromium steel 08Ch13 (1.4000, X6Cr13) under these
conditions is quoted as 0.14–0.2 mm/a (5.51–7.87 mpy). Like other chromium
steels, it also tends to undergo pitting corrosion, and for this reason cannot be used
under such conditions [280]. For comparison, the steel 3 is attacked at a rate of
3.7–4.5 mm/a (146–177 mpy) in the lower part of the tank and 1.5–2.0 mm/a
(59.1–78.7 mpy) in the upper part, but does not succumb to pitting corrosion.

– High-temperature corrosion behavior in SO2-containing gases –

Corrosion studies over a period of 8,600 h in the production of sulfuric acid showed
that the chromium steels are highly suitable under the following conditions: at a
temperature of 873 K (600
C) in a gas mixture of 4.5 % SO3, 2 % SO2, 0.02 % H2O
and 3–5 mg/m3 HF. The corrosion rate of a chromium steel with 12–14 % Cr (with-
out Mo) in the contact apparatus was 0.02 mm/a (0.79 mpy). In the heat exchanger at
723 K (450
C) with a content of 7.5 % SO3, 0.2 % SO2, 0.02 % H2O and 3–5 mg/m3
HF in the gas stream, the corrosion rate on this steel after the same test duration
was 0.07 mm/a (2.76 mpy). Chromium-nickel steels containing 22–25 % Cr,
26–29 % Ni, 2.5–3 % Mo and 2.5–3 % Cu show better corrosion rates of about
0.001 mm/a (0.04 mpy) and below under these conditions [237].
The high-temperature resistance of a material increases as the chromium content
increases, as can be seen from Figure 61. A reasonable corrosion resistance is
achieved already at a temperature of 1,073 K (800
C) under an SO2 partial pressure
of 2.5  10–3 MPa with a chromium content of 5 %. Above this content, it increases
only slightly under the conditions of an argon atmosphere [205].
Under the influence of oxygen, metals form oxides, the rate of formation of
which increases as the temperature rises. Iron- and nickel-based alloys with more
than 15 % chromium form an almost pure chromium oxide layer on their surface
under these conditions. By suitable choice of the alloy composition and the addi-
tional effect of various special additives, such as silicon and rare earths (cerium,
lanthanum or yttrium), this chromium oxide layer becomes very dense and adheres
firmly to the surface, so that the latter is protected from further oxidation. These
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 A 19 Ferritic-austenitic steels with more than 12 % chromium 137

alloys are used as heating conductors, including ferritic heating conductors with
chromium and aluminium as alloying addition, such as Fe-25Cr-5Al, Fe-20Cr-5Al
and X 7 CrAl 14 4. In spite of the high chromium content, they form practically
pure aluminium oxide (Al2O3) on their surface when exposed to heat. The protective
effect of this harder and brittle oxide during uninterrupted operation is better than
that of the chromium oxide of the austenitic heating conductors, which is why ferri-
tic heating conductors can be used up to significantly higher temperatures than the
latter. Because of its brittleness, the Al2O3 layer is very sensitive to changes in tem-
perature and mechanical influences. These peculiarities should be taken into
account when these materials are used.
Aggressive gases such as sulfur dioxide, carbon monoxide and acid vapors can
impede this oxide formation on the surface of the material and in this way consider-
ably reduce the service life of the material [31].
High-temperature corrosion experiments on iron-chromium alloys with increas-
ing nickel content at 973 K (700
C) in an oxygen/sulfur dioxide gas mixture in a
ratio of 4 : 1 demonstrate the good, high-temperature corrosion behavior of FeCrNi
alloys. The best corrosion resistance under these conditions after a test duration of
500 h is shown by an iron-chromium alloy with 25 % Cr and additions of 2.54 % Al
and 1.55 % Zr. Table 44 contains the materials investigated, Table 45 the weight
increases after various times and Figure 76 a graph of the results. These graphs
show that in an atmosphere containing sulfur dioxide at 973 K (700
C), the good,
high-temperature corrosion resistance of chromium-containing iron materials is
improved further by alloying additions. The high-temperature corrosion behavior in
such an atmosphere at 973 K (700
C) is impaired by addition of nickel [278]. If the
test temperature is increased from 973 to 1,173 K (700 to 900
C), the pattern of
resistance in this atmosphere changes. The corrosion on the chromium alloys
increases, as can be seen from Table 46 and Figure 77. After a test duration of 500 h
under these conditions, protective oxide layers are formed on the surface of the ni-
ckel-containing materials after a test duration of 200 h. The scaling proceeds in
accordance with a parabolic time law, while corrosion of the iron-chromium alloy
proceeds linearly, and no protective action occurs. The alloy 3 from Table 44 contain-
ing chromium and 23.4 % Ni shows the best resistance in this case [278].
Figure 78 shows the corrosion rates of chromium-molybdenum steels with var-
ious molybdenum contents and an increasing chromium content and of 18 8 chro-
mium-nickel steel on exposure to a flue gas containing 250 ppm SO2, 2,000 ppm
HCl, 30 % H2O and air at various temperatures. Under this exposure, chromium-
molybdenum steels with 9 % Cr and 1 % Mo are the most resistant materials up to
473 K (200
C), although their corrosion rates are about 3 mm/a (118 mpy) at 450 K
(177
C). According to this graph, both types of steel show inadequate resistance
under these conditions. It should be remembered that the results originate from an
experiment only 192 h in duration. Figure 79 shows the corrosion behavior of the
materials described (see Figure 78) in the flue gas as the temperature rises. The
material consumption increases rapidly as the temperature rises, and decreases as
the chromium content increases. The chromium content does not improve the cor-
rosion resistance of the materials in flue gases containing HCl or chloride [67].
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138 Sulfur Dioxide

Figure 76: Mass gain increase of iron alloys (Table 44) at 973 K (700
C) in an O2/SO2 (4 : 1)
atmosphere as a function of time. For the test data, see Table 45 [278]
1) Ni-25Cr
2) Ni-25Cr-2.5Al-1.5Zr
3) Fe-25Cr-48Ni-2.5Al-1.5Zr
4) Fe-25Cr-23Ni-2.5Al-1.5Zr
5) Fe-25Cr-9Ni-2.5Al-1.5Zr
6) Fe-25Cr-2.5Al-1.5Zr

Alloy Graph Alloy Chemical composition, %

No.* No.**
Ni Fe Cr Al Zr

Fe-25Cr2.5Al1.5Zr ¯ 1 0 70.8 25.0 2.54 1.55

Fe-25Cr9Ni2.5Al1.5Zr ˜ 2 8.9 bal. 25.1 2.55 1.57

Fe-25Cr23Ni2.5Al1.5Zr ˆ 3 23.4 47.1 25.1 2.65 1.63

Fe-25Cr48Ni2.5Al1.5Zr ´ 4 bal. 23.3 24.8 2.61 1.59

Ni-25Cr2.5Al1.5Zr ` 5 bal. – 25.3 2.52 1.59

Ni-25Cr
6 75.0 – 25.0 – –

Fe-25Cr 7 – 75.0 25.0 – –

* the numbering applies to Figures 76 and 77

** the numbering applies to Tables 45 and 46

Table 44: Chemical composition of alloys used in corrosion studies at 973 and 1,173 K (700 and
900
C) in an O2/SO2 atmosphere (4 : 1) [278] (see also Tables 45 and 46 and Figures 76 and 77)

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 A 19 Ferritic-austenitic steels with more than 12 % chromium 139

Test duration, Weight increase, mg/cm2

h (for the alloy numbers, see Table 44)

1 2 3 4 5 6 7

1 0.13 – 0.15 0.2 0.53 – –

15.5 – – – 0.37 1.37 – –

45 0.25 0.13 0.16 0.15 2.2 20.1 0.25

72 0.17 0.18 1.8 2.2 2.7 37.6 0.8

144 0.3 0.87 2.5 3.8 5.6 36.2 0.8

267 0.78 0.71 1.5 5.3 21.4 33.0 1.1

500 1.0 1.3 3.6 6.5 38.9 24.8 8.1

Table 45: Weight increase of alloys in an O2/SO2 atmosphere (4 : 1) at 973 K (700
C) (for the
graph, see Figure 76) [278]

Test duration, Weight increase, mg/cm2

h (for the alloy numbers, see Table 44)

1 2 3 4 5 6 7

72 0.04 0.6 0.6 0.58 0.94 0.88 0.85

146 0.65 0.86 0.84 0.86 1.11 0.38 1.12

266 2.64 1.7 0.95 0.92 0.96 0.62 1.35

500 3.40 1.85 1.01 1.0 1.39 – –

Table 46: Weight increase of alloys in an O2/SO2 atmosphere (4 : 1) at 1,173 K (900
C) (see Fig-
ure 77) [278]

Considerable pitting corrosion can be expected in this flue gas if the temperature
falls below the dew point, especially on CrNi steels.
During an operating period of 1,419 h and a downtime of 285 h in a gas washing
plant, the chromium steel type 430 showed a corrosion rate of less than 0.025 mm/a
(0.98 mpy) at a flue gas intake temperature of 394–410 K (121–137
C). The flue gas
consisted of (percent by volume) 0.29 SO2, 0.03 SO3, 12.5 CO2, 74.6 N2, 4.9 O2,
7.7 H2O and 106–247 g/m3 flue ash. The flow rate of the flue gas was 9–10 m/s and
the throughflow 76 m3/min [78, 79]. The material specimens were at the inlet to the
intermediate heater.

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140 Sulfur Dioxide

Figure 77: Mass gain of iron alloys (Table 44) at 1,173 K (900
C) in an O2/SO2 (4 : 1) atmosphere
as a function of time. For the test data, see Table 46 [278]
2) Ni-25Cr-2.5Al-1.5Zr
3) Fe-25Cr-48Ni-2.5Al-1.5Zr
4) Fe-25Cr-23Ni-2.5Al-1.5Zr
5) Fe-25Cr-9Ni-2.5Al-1.5Zr
6) Fe-25Cr-2.5Al-1.5Zr

Figure 78: Corrosion rates of Cr steels and chromium-nickel steels in a flue gas with a composi-
tion of 250 ppm SO2, 2,000 ppm HCl, 30 % H2O and air at various temperatures. Flow rate 10 l/h,
test duration 192 h [67]
s 1Cr-0.5Mo, 2.25Cr-1Mo, 5Cr-0.5Mo
d 9Cr-0.5Mo
h 18 8 CrNi steel (SUS 304; cf. 1.4301, AISI 304)

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 A 19 Ferritic-austenitic steels with more than 12 % chromium 141

Figure 79: Corrosion rates of iron materials as a function of the chromium content at various
temperatures in a flue gas (250 ppm SO2, 2,000 ppm HCl, 30 % H2O and air). Flow rate 10 l/h, test
duration 192 h [67]

During combustion of various fuels, deposits of varying composition form on the

materials as can be seen from Table 26. In an oxygen test atmosphere containing
0.15 % SO2, turbine blade materials are attacked to varying degrees. At a tempera-
ture of 703 to 903 K (430 to 630
C), the chromium steel containing 25 % Cr, 4 % Al
and 1 % Y has a relatively good resistance, with depths of attack of not more than
87 lm after a test duration of 1,000 h. It exhibits hardly any attack up to 843 K
(570
C) with deposits of the type A according to Table 26.
The corrosion rate increases after 1,000 h to 22 lm at 863 K (590
C) and to 87 lm
at 913 K (640
C), and reaches a maximum of 214 lm at 973 K (700
C). At 1,144 K
(871
C), penetration depths of only 19 lm are reached in the material. A dense
scale layer which withstands further corrosion forms on the material. The most
severe corrosion attack under these conditions in the gas mentioned can be expected
with deposits of type C according to Table 26, particularly at 913 K (640
C). The
penetration depth in this case is 483 lm after a test duration of 1,000 h [129]. The
combustion residues formed by the fuels are decisive for the corrosion behavior of
the materials used, as can be seen from Table 27.
The flue gas deposits in heat recovery plants in garbage incineration differ quite
considerably. [207] contains a summary of the values from various plants. The corro-
sion rates on the heating surfaces of chromium steel of the type 446 (1.4762,
X10CrAlSi25) are less than 3 mm/a (118 mpy) at temperatures of 422 to 589 K (149
to 316
C) and between 3 and 6.1 mm/a (118 and 240 mpy) at 589–922 K
(316–649
C). This steel tends to undergo pitting corrosion in the presence of moist
deposits [207]. Corrosion rates of 0.23 to 0.33 mm/a (9.06 to 13.0 mpy) are quoted in
this source for the above steel 446 in a flue gas (no precise composition) in the tem-
perature range between 1,144 and 1,255 K (871 and 982
C) [207].
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142 Sulfur Dioxide

The corrosion of chromium steels under deposits which form on the material dur-
ing combustion of conventional fuels has already been described in Section A 17.
Electrochemical studies led to the results in Figure 73. A medium consisting of
(mol/mol) 0.78 Li2SO4, 0.135 K2SO4 and 0.085 Na2SO4 with a melting point of 816 K
(543
C) was used. As can be seen from Figure 73, the resistance of these steels
to alkali metal sulfate corrosion increases as the chromium content increases.
Figure 80 shows the influence of gases, in particular SO2, on the corrosion behavior
of steel 4 (see Figure 73) containing 18 % Cr, 0.25 % Ni, 1.45 % Al, 0.20 % Mo,
0.70 % Si, 0.74 % Mn, 0.09 % C, 0.013 % P and 0.009 % S. It can be seen from this
figure that sulfur dioxide stimulates corrosion in the transpassive region, while the
presence of O2 in the melt inhibits this. Experiments at UAg = –0.4 and 0.1 V have
shown that the material consumption rates no longer increase with an increase in
the SO3 concentration of 1–10 percent by volume [265].
Corrosion studies in a gas mixture of 65–80 % SO2, 1–3 % O2, up to 1 % SO3, up to
0.5 % H2O and N2 as the balance in the temperature range 873 to 1,073 K (600 to 800
C)
confirm the better corrosion behavior of chromium steels compared with chromium-
nickel steels of the type 18 8. Si- and Al-containing chromium steel is most resistant
under these conditions. At 923 K (650
C) it shows a corrosion rate, when converted, of
4.5 mm/a (177 mpy) at a corrosion penetration depth into the material of 0.09 mm
after a test duration of 180 hours (see Tables 47 a and 47 b) [279].

Figure 80: Influence of the gas phase on the dependence of the material consumption of steel 4
(see Sections A 17 and A 18), containing (%) 18 Cr, 1.45 Al, 0.74 Mn, 0.70 Si, 0.20 Mo amongst
others, on the potential in an alkali metal sulfate melt ((mol/mol) 0.78 Li2SO4, 0.135 K2SO4, 0.085
Na2SO4) at 973 K (700
C) (potentiostatic holding test over 23 h) [265]
s N2, d O2, e O2/SO2 + 1 percent by volume SO3

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 A 19 Ferritic-austenitic steels with more than 12 % chromium 143

Iron-chromium alloys show quite a good corrosion behavior under the conditions
of water-cooled gas turbines exposed to salt melts in a medium containing sulfur
dioxide, as can be seen from Figure 33 and Table 24.
In corrosion studies over 1,000 h at 863 K (590
C), relatively low penetration
depths and corrosion losses were found overall on specimens of iron-chromium
alloys which were sprayed 3 times a week with 1–2 mg/cm2 salt ((mol/mol)
0.01 PbSO4 + 0.15 K2SO4 + Na2SO4 as the balance). The studies were carried out in a
furnace atmosphere consisting of 0.15 % SO2, 76 % O2 and N2 as the balance, at a
flow rate of 0.85 l/h.
The experimental alloy HT-5 (Fe-30Cr4Al1Y) is comparable in its high-tempera-
ture corrosion resistance to the nickel-chromium alloy HT-11 (Ni-30Cr) [134].

– Flue gas desulfurization –

Chromium steels tend to undergo pitting corrosion in almost all the plant compo-
nents of flue gas desulfurization plants [216].
The ferritic-austenitic steel G-X 3 CrNiMoCuN 24 6 (9.4460), including its var-
iants, has proved to be a particularly suitable material for suspension pumps. Under
these conditions, it has a very good resistance to pitting corrosion and stress corro-
sion cracking, as well as erosion corrosion [558, p. 166 et seq.].
Corrosion studies in the flue gas washing solutions (see Table 48) of a coal-fired
power station were carried out on the ferritic-austenitic cast steel 9.4462 (G-X 3
CrNiMoCuN 26 6 3). The analyses relate to the solid-free filtrate.

Material Chemical composition, %

C Cr Al Si Ni Ti Mn S P

Ch18N12T 0.05 17.50 – – 11.8 0.40 0.38 0.011 0.012

Ch13S 0.03 12.83 0.31 1.20 – – 0.20 0.021 0.006

Ch13Yu 0.03 13.16 1.78 0.05 – – 0.20 0.023 0.005

Ch13YuS 0.02 13.82 1.60 1.69 – – 0.23 0.010 0.009

Ch13YuST 0.03 12.12 1.78 1.54 – 0.36 0.24 0.020 0.005

Ch13S2Yu2BT* 0.04 13.0 1.75 1.42 0.93 0.41 0.35 0.008 0.024

* 0.93 % Nb

Table 47a: Chemical composition of chromium and chromium-nickel steels for high-temperature
corrosion studies in a hot gas mixture (65–80 % SO2, 1–3 % O2, up to 1 % SO3, water vapor up to
0.5 %, N2 as the balance) at temperatures of 873–1,073 K (600–800
C), for the results see
Table 47b [279]

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 144 Sulfur Dioxide

Material Test temperature, K (
C)

873 (600) 893 (620) 923 (650) 953 (680) 973 (700) 1,023 (750) 1,073 (800)

Ch18N12T 160.32/ 351.6/ 900/ *

0.20 0.44 1.13

Ch13S 78.56/ 100.96/ 194.44/

0.098 0.137 0.243

Ch13Yu 120.35/ 260.3/ 510.6/

0.150 0.325 0.638

Ch13YuS 83.09/ 227.13/ 463.37/

0.104 0.283 0.580

Ch13YuST 173.28/ 351.20/

0.216 0.439

Ch13S2Yu2BT 75.63/ 296.8/ 342.3/

0.09 0.37 0.427

* 2.2 mm-thick specimen completely destroyed

Table 47b: Results of corrosion studies on various chromium and chromium-nickel steels (see
Table 47a) in a gas mixture containing sulfur dioxide (65–80 % SO2, 1–3 % O2, up to 1 % SO3, H2O
up to 0.5 %, N2 as the balance) at various temperatures. Numerator: material consumption in
mg/cm2, denominator: penetration depth of the corrosion after a test duration of 180 h in mm
(1 mg/cm2 = 0.06 mm/a) [279]

Solid pH Chloride Sulfate Nitrite Nitrate

Absorber tower 241.0 g/l 6.41 25,185 ppm 64 ppm 0.5 ppm 80 ppm

Oxidation tower 102.2 g/l 4.30 31,102 ppm 58 ppm 1.0 ppm 250 ppm

Concentrator 696.1 g/l 5.69 21,904 ppm 47 ppm 0.5 ppm 60 ppm

Table 48: Composition of the flue gas washing solutions of a coal-fired power station [643]

The pH was reduced to 4 or 2 for some studies by addition of sulfuric acid. The
chloride content was increased to 110,000 ppm by addition of CaCl2. The results of
the studies showed a good resistance of the cast steel 9.4462 towards erosion corro-
sion and pitting corrosion in the flue gas washing solutions investigated up to a
chloride content of about 40,000 ppm in the temperature range 323 to 343 K (50 to
70
C) in the given suspensions with flow rates of up to 4 m/s. Use as a material for
fittings under the conditions presented by the flue gas washing solutions of the
above composition is conceivable. Its use is also justified at chloride contents of up
to 110,000 ppm and pH values above 4 if the chloride content is not substantially
above 50,000 ppm and peak values above 100,000 ppm are reached in not more than
10 % of the operating time. Its use is not to be recommended at lower pH values,
for example about 2. Possible crevice corrosion should be prevented by the construc-
tional design [643].
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 A 20 Austenitic chromium-nickel steels 145

These materials are currently finding increasing interest in chemical process

technology, so that their use in flue gas desulfurization plants is worth considering.

– Corrosion protection measures –

The air compressor blades of industrial gas turbines were destroyed by corrosion
fatigue cracking. The steel X20Cr13 (1.4021, AISI 420) was used as the material.
Chemical analysis of the deposits on the blades showed aggressive, corrosion-pro-
moting constituents such as chlorides, sulfates and iron-III compounds, as well as
low pH values down to 3. The analyses of the intake air showed that it contained
traces of SO2, SO3 and chlorides, which can accumulate to high concentrations in
the deposits. Sulfuric acid forms as a result of atmospheric oxidation of the SO2, and
together with chlorides this leads to pitting corrosion on the steel X20Cr13. Once a
pit has formed, the conditions exist for fatigue corrosion cracking due to the notched
effect in the hole in association with the alternating mechanical stresses during
operation. Protective coatings of Skaphen (unsaturated polyester) have proved to
be a good protection against this type of corrosion [281].
Preoxidation of chromium steels with a chromium content of 20 % does not have
the positive result of those containing 10 % Cr. As a result of the high chromium
content, a protective oxide layer with a thickness of 2–4 lm forms on the surface
after an exposure time of 500 h in an argon atmosphere containing 10 % SO2 at
1,073 K (800
C).
After preoxidation of 1 min in air with a moisture content of 600 ppm at a flow
rate of 70 cm/min at 1,073 K (800
C), an oxide layer of 3–5 lm forms on the surface
of the 20 % chromium steel after 140 h in an argon atmosphere containing 10 %
SO2 [264].
The dispersion-hardened iron-chromium alloy DT 3608Y005 containing 13 % Cr,
1.5 % Mo, 3.6 % Ti, 0.8 % O (bound to titanium) and 0.5 % Y2O3 has a good resis-
tance to high-temperature corrosion at 873 K (600
C) in a combustion gas contain-
ing 2 % SO2. After a test duration of 700 h in this gas, the weight increase is less
than 2 mg/cm2 [282]. This material is distinguished by good mechanical properties
up to 973 K (700
C).

A 20 Austenitic chromium-nickel steels

The austenitic chromium-nickel steels also owe their good corrosion resistance to
the formation of passive layers on the surface, and maintenance or renewal of these
layers. In cases where this protective layer is destroyed, more severe corrosion can
be expected.
The austenitic chromium-nickel steels are not attacked by dry, gaseous and anhy-
drous, liquid sulfur dioxide (see Introduction – Corrosive behavior –).
The corrosion of metallic materials in liquefied sulfur dioxide increases with the
water content. No noticeable corrosion was found on an 18 8 CrNi steel after two

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DOI: 10.1002/9783527610433