Materials and Corrosion 2005, 56, No.
7 Superheater corrosion in a CFB waste boiler
Field test of superheater corrosion in a CFB
waste boiler: Part I – Metal loss characteristics
The corrosion was investigated on a superheater test coil in a
CFB waste boiler. The alloys ranged from ferritic steel T22 to ni-
ckel-based Alloy 65 and the metal temperatures were between 460
and 540 8C. The thickness of the deposit was alloy and temperature
dependent. The low-alloyed steels developed thick deposits at all
temperatures while the deposit thickness increased with the tem-
perature on the high-alloyed steels and the nickel-based alloy.
The corrosion attack was alloy dependent and related to the deposit
1 Introduction
The corrosive environment in biofuel combustion is gener-
ally worse than when fossil fuels are burnt. This is particularly
valid for the combustion of waste that is considered to be a
biofuel, either it is in the form of Municipal Solid Waste
(MSW) or Refuse Derived Fuel (RDF). In biofuel combustion
large amounts of deposits may form on the superheater tubes
and other surfaces. The deposit formation depends on e.g. the
flue gas and metal temperatures, as well as the flue gas com-
position and flow. The deposit formed limits the efficiency of
the boiler. First, the heat transport between the gas and the
produced steam is limited. This effect is referred to as fouling.
Second, the deposits may induce rapid corrosion mechanisms
leading to tube failure. To avoid this, the steam temperatures
must be kept substantially lower than in combustion of fossil
fuels.
The operating temperature of the boiler depends among
other things on the kind of biomass that is burnt. Apart
from waste, it may be e.g. peat, straw, woodchips, etc. The
deposit forming elements in these fuels are mainly S, Cl,
O, K, Na and Ca. The danger of corrosion attack has been
observed to correlate to the ratio between the chlorine and
the sulphur contents in the fuel [1]. The higher this ratio is,
the more severe is the corrosion. Among the biofuels, waste
often has a high Cl/S ratio and it frequently gives a corrosive
environment in the boiler. Waste is sometimes mixed with
other fuels to decrease the corrosivity, leading to decreased
Cl/S ratio [2, 3]. Furthermore, MSW sometimes contains
high levels of elements such as Pb, Zn and Sn that can be en-
riched in the deposit. Chlorides of these heavy metals may,
together with alkali chlorides, form eutectic chloride melts
at low temperatures that will increase the corrosion rate
[4 – 8].
* M. Norell, P. Andersson,
Materials and Manufacturing Technology,
Chalmers University of Technology,
S-412 96 Göteborg (Sweden)
E-mail: mats.norell@me.chalmess.se
F 2005 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
449
P. Andersson and M. Norell*
crest. The nickel-based Alloy 65 was preferentially attacked di-
rectly under the crest of the deposit while the other alloys were pre-
ferentially attacked at the edge. The corrosion rate increased with
temperature for X20, Alloy 304L, Alloy 310 and Alloy 825; de-
creased on Alloy 65; and was bell shaped on T22 and Alloy 28.
Alloy 310 suffered from severe pitting corrosion in a line following
the edge of the deposit crest. The best overall corrosion resistant
alloy was Alloy 28.
Waste combustion is done primarily for two reasons; waste
disposal and energy conversion. Waste disposal by incinera-
tion reduces its volume and thus the need for landfilling. For
long times it has been attractive to combine the disposal of
waste with the recovery of its energy content as heat. Further-
more, as a biofuel, waste is not considered to give any net
emission of CO2 that would contribute to global warming. In-
creasing electricity cost is a further driving force to convert
the produced heat into electricity. This conversion has created
a demand for increased steam temperatures and thus metal
temperatures in the superheaters. Today the steam temperature
is limited by the corrosion attack [1, 9 – 10]. The corrosion
rate, burning MSW, has been observed to increase rapidly
at metal temperatures above 300 8C [9 – 10]. This has, for ex-
ample, made Japan avoid steam temperatures above 300 8C
until 1995 [11]. Today, steam is produced at temperatures
up to about 450 8C in waste boilers around the world [1,
12]. As a comparison, alloy development for steam turbines
is now aiming at 650 8C or even 700 8C to improve the thermal
efficiency of turbines [13]. Ideally, the steam produced in
waste combustion should be equally hot.
The boiler design is an important approach to compete
against the corrosion problems in waste combustion. How-
ever, it must be combined with an appropriate choice, or de-
velopment, of alloys. This calls for deep knowledge of the cor-
rosion in the boiler. The problem is complex. The composition
of the fuel, flue gases and deposits formed are examples of
factors that both vary between different boilers and fluctuate
with time. Hence, research about corrosion in waste boilers
combines several approaches ranging from evaluation of field
experience, via field tests of various kinds to laboratory ex-
periments. The field tests, in their turn, range from separate
probes that are inserted at available ports to large scale test
sections that are built in at ordinary positions. The previous
approach is flexible and less costly. It can be used e.g. to com-
pare the corrosion between different boilers. However, the
samples are usually limited to small rings that give limited
information about the corrosion and the probes are not tested
at ordinary tube positions. Thus, the corrosion on a probe may
not be the same as in the boiler. The larger test sections basi-
cally have opposite characteristics on all these points. The
samples are test tubes that can give extensive and representa-
DOI: 10.1002/maco.200403852
450 Andersson and Norell
tive information about the corrosion in the boiler. Since they
are tested at normal tube positions the flue gas flow pattern,
conditions for deposit build up and other factors are charac-
teristic for the boiler. Whatever test method, the reported cor-
rosion rates are often limited to the deepest thickness reduc-
tion. This can be sufficient to classify the alloys, but it only
gives a moderate description of the corrosion attack. For in-
stance, the most severe corrosion on superheater tubes is nor-
mally expected at the edge of the deposit crests, but there are
only few systematic quantitative examinations whether this is
the case [4, 14].
Candidate alloys for waste boiler superheaters range from
ferritic and martensitic steels to austenitic steel and advanced
nickel-based alloys. Extensive field tests of different alloys
have been done in Japan during the last years, especially
by Kawahara and co-authors [15 – 17]. They have found
that the corrosion resistance increases with the sum of the
Cr, Ni and Mo contents. The effect of alloying was stronger
the more corrosive was the environment. Probe tests in diffe-
rent boilers showed that a CrþNi content of approximately
80% gave the best corrosion resistance [15]. Latter field tests
gave the best performance for Ni-base alloys with high
amounts of Mo (19%) in the most corrosive locations (high
Cl-content in the deposits at 550 8C). However, besides being
costly, such alloys are not a universal solution to the corrosion
problems in waste combustion. For instance, Alloy 600
(72Ni16Cr) may suffer from severe pitting [18]. In the present
study, it will be shown that a Mo-containing Ni-base alloy cor-
roded more then less alloyed materials, especially at lower
temperatures. Many of the alloys studied here were tested
as composite tubes combining a ferritic core and a high-alloy
outer layer. This gives a possibility for favourable combina-
tion of creep strength, weldability and corrosion resistance,
etc. Field experience regarding composite tubes has been re-
ported in the literature [4].
In this study, a field test was done in a Circulating Fluidised
Bed (CFB) burning RDF. The aim was to investigate the cor-
rosion of different alloys in a realistic flue gas flow and in a
temperature range (460 – 540 8C) that was higher than normal
in waste boiler superheaters today, but relevant for the future.
For this purpose, a test coil was inserted in the top of the back
pass. Alloys ranging from ferritic to nickel-base were tested
for one month. Also, the corrosion in the waterwall was ex-
amined in the field test. Results from that study have been
published previously [19].
The paper is divided in two parts. This paper, part 1, con-
centrates on the metal loss of all seven alloys tested. In order
to get a detailed picture of how the corrosion attack differed
between the alloys the thickness reduction was measured both
around and along the test tubes. The attack was correlated to
the position of the deposit crest and the tube temperature. The
test tubes were also long enough (380 mm) to get representa-
tive data not only from the thickness reduction but also from
the weight loss. Furthermore, the amount of deposit formed
was estimated to see how it related to the temperature or com-
position of the alloys as well as to the corrosion.
The second part of this paper will present an in-depth de-
scription of the corrosion of four selected alloys from the test
with significantly different corrosion behaviour. The deposits
and oxides formed on these alloys have been characterised.
That paper will attempt to analyse more in detail what factors
or reactions that determined the attack of the alloys.
Materials and Corrosion 2005, 56, No. 7
2 Experimental
2.1 Field test
The field test was conducted for 738 h in a CFB-boiler at
Korstaverket in Sundsvall, Sweden. The boiler consists of the
fluidized bed, followed by a cyclone that separates the parti-
cles and reintroduces them into the bed. After the cyclone lies
the upper draw with superheater tubes. The boiler was built in
1984 and external systems were modified in 1995. In normal
operation, the boiler is burning a mixture of 60% RDF and
40% woodchips. During the field test, the boiler was burning
RDF only. The boiler capacity is 5.5 ton RDF per hour pro-
ducing 28 ton steam at 33 bar/ 285 8C. The fuel was shredded
and samples were collected throughout the test. These col-
lected samples were blended and 0.5 kg of the blended fuel
sample was analysed. A detailed analysis of the flue gas com-
position in the furnace is found in the paper about the corro-
sion in the waterwall [19].
The test coil was inserted in the upper draw at the top of the
back pass, on candidate, but not ordinary, superheater posi-
tions. A schematic view of the coil is shown in Fig. 1. The
superheater test coil constituted a separate steam circuit.
The coil consisted of two layers. The top layer served primar-
ily to heat up the steam to a higher temperature than in the
ordinary superheater of the boiler. This layer was also in-
tended to shield the test tubes from the direct impact of
flue gases and particles. The test tubes were situated in the
lower layer. Prior to the field test it was observed that the de-
posit formation was very limited in one quarter of the section
where the coil should be inserted. This was probably related to
the flue gas flow pattern in the boiler. Aiming to expose the
test tubes to as equal conditions as possible no test tubes were
mounted in this region. A soot blower was situated in the
upper draw. However, it was mounted at least 1.5 m above
the test coil so it is not expected to have had any major influ-
ence on the deposit formation, nor on the corrosion.
The alloys were tested in a metal temperature gradient ran-
ging from 460 8C to 540 8C. The metal temperatures of the
tubes were monitored by four thermocouples that were sol-
dered in the tube wall on the outer side, c.f. Fig. 1. Linear in-
ter- and extrapolations were used to estimate the metal tem-
peratures of individual test tubes. All alloys were tested at
Fig. 1. Schematic view of the superheater test coil in the upper
draw. The metal temperature and test tube positions are indicated.
Thermocouple locations are indicated T
Materials and Corrosion 2005, 56, No. 7 Superheater corrosion in a CFB waste boiler 451

three different temperatures except alloy T22 that was tested

at six temperatures.
The tested alloys ranged from ferritic Fe2Cr1Mo and mar-
tensitic Fe10Cr steels to the nickel-based Alloy 65. Though
the alloys T22 and X20 might not be considered candidate
alloys for these advanced conditions, they are commonly
used in many boilers and important as references. The com-
position of the alloys is shown in Tab. 1. The test tube length,
diameter and wall thickness were 380 mm, 44.5 – 54.0 mm
and 4.5 – 6.0 mm, respectively.
When the test was interrupted air was blown in the boiler
during cooling to avoid aqueous corrosion. After cooling the
test tubes and their environment were photographed and
roughly characterised. Deposit and ash samples were col-
lected and the test coil was removed. All tubes and samples
were stored in a sealed box containing silica gel to minimise
the hydration of the samples and avoid spallation of the de-
posit during storage.
2.2 Evaluation
Sections were prepared of all test tubes for subsequent ana-
lysis of the scale and deposit formation by using SEM and
other methods. The deposits were first mechanically fixed
to the tubes with epoxy where the sections were cut. They
were taken a few centimetres away from the welds between
the test tubes to avoid the heat affected zone. The results of
these analyses will be presented in part two of this paper.
The remaining tube, approximately 250 mm long, was used
to characterise the metal loss. All deposit and corrosion pro-
ducts were removed by the use of a 600 bar water jet. After
cleaning, approximately 1 lm of oxide remained on the tubes.
High precision measurements of the weight and length of
the tubes were done before the test coil was built, and again
after cleaning. The weight loss per length unit was converted
to an equivalent average corrosion rate of the entire tube sur-
face. The accuracy of the measurement was equivalent to
about 90 lm/year.
The thickness reduction was measured around the tubes to
get a quantitative description of how the tubes had been at-
tacked. The remaining wall thickness was determined by
using a dial tube gauge and compared to that of unexposed
tubes. The accuracy in each measurement was about
0.05 mm, equivalent to 0.6 mm/year. The thickness loss
was measured in 12 sectors at 308 intervals around the tubes.
The top layer of the test coil splitted the fuel gas flow so that
Fig. 2. Schematic view of the split deposit for-
mation. The tube sectors were indexed from the
highest deposit crest
two deposit crests were sometimes formed on the test tubes,
c.f. Fig. 2. Since the flue gas flow was not perpendicular to the
test coil one of the crests were higher than the other. The es-
timated direction of the highest crest was indexed as the sector
at 08, with an uncertainty of
308. Ten thickness measure-
ments, about 10 mm apart, were done along a line in each sec-
tor. The average from the ten points was then used to describe
how the attack varied around the tubes as showed in circular
diagrams below. The deepest sector average was used to com-
pare the corrosion rate of the alloys. Additionally, the deepest
(i.e. thinnest) point was determined on each tube. It was usual-
ly found in the deepest sector.
3 Results
3.1 Environment
The test was run for a month. However, the boiler was shut
down twice during that period for reasons external to the test.
The test coil was kept at temperature for 738 hours. Still, there
were some temperature fluctuations during this period. Some
occasional temperature drops of at the most 120 8C occurred
lasting a few minutes. Once the temperature rose with 100 8C.
The temperatures were constantly oscillating about
10 8C.
After half the test period the thermocouples were broken. So
far there was no indication that the metal temperature was de-
creasing due to the deposit formation. Throughout the test the
temperature of the outgoing steam was kept constant at
500 8C. The average test tube metal temperatures, as estimated
from the thermocouples, are indicated in Fig. 1.

Table 1. Chemical composition (wt-%) of the tested alloys according to melt analyses. Fe is balance.

Alloy C Cr Ni Mo Si Mn Others

T22 0.12 2.06 1.0 0.3 0.6

X20 (X20CrMoV121) 0.18 10.3 0.47 0.8 0.3 0.8 0.2Cu 0.3V
Alloy 304L 0.01 18.3 10.1 0.4 1.2
Alloy 310a 0.02 25.4 21.1 0.1 0.4 1.7 0.1Cu
Alloy 28a,b 0.01 26.7 30.4 3.3 0.4 1.6 0.9Cu
Alloy 825 0.01 22.4 39.5 3.2 0.4 0.2 2.0Cu 0.1Al
0.7Ti 0.5Co
Alloy 65a,b 0.01 20.7 61.3 8.3 0.4 0.4
[a] Composite tubes
[b] These alloy tradenames are Sanicro 28 and Sanicro 65, respectively
452 Andersson and Norell Materials and Corrosion 2005, 56, No. 7

Table 2. Content of some elements in the previously dried fuel sample. The sample humidity was 6.3 wt-%

Element wt-% Element wt-% Element wt-% Element wt-% Element mg/kg Element mg/kg
Ash 15.4 S 0.16 Ba 0.02 P 0.13 Pb 133 Cu 225
Al 1.35 Mn 0.03 Na 0.93 Cl 0.42 Cd 1.6 Ni 35
Si 3.70 Mg 0.25 K 0.43 F 0.01 Co 10 V 9
Fe 0.38 Ca 1.99 Ti 0.14 Br < 0.01 Cr 55 Zn 425

Refuse Derived Fuel is very inhomogeneous. Therefore,
though the fuel was shredded and samples were collected
throughout, the analysis, c.f. Tab. 2, only gives an indication
of the fuel composition.
Collected samples of the deposits were analysed by means
of XRD. Independent of the alloy or the temperature the bulk
of the deposits consisted mainly of alkali chlorides and calci-
um sulphate. This is in agreement with a previous analysis of
these deposits [20]. The composition of the deposits will be
discussed a bit more in detail in part two of this paper.
At the visual inspection of the test coil, it was strikingly
clear that the deposit formation was alloy dependent. The de-
posit height varied between the test tubes from a few milli-
metres to several centimetres. The changes were incremental
were the tubes were joined. Fig. 3 shows the height of the de-
posit crests as measured on tube sections. Though there is sub-
stantial scatter in the data, two trends can be observed. First,
the deposit thickness increased with the temperature, at least
for the high-alloyed materials. Secondly, thicker deposits
were formed on the ferritic/martensitic steels than on the
high-alloyed materials.
3.2 Metal loss

3.2.1 General

Fig. 3. The height of the deposit crests on the test tubes
The corrosion rates were very high for all alloys. The poor-
est tube would probably have been broken if the test had lasted
one or two weeks more. The rates ranged from 1.8 mm/year
for high-alloyed austenitic steel Alloy 28 at 462 8C to 34 mm/
year for the ferritic steel T22 at 516 8C. The corrosion rates are
summarised in Figs. 4 and 5. They are presented in mm/year
though this does not imply that the rate should be linear for so
long times. Fig. 4 shows the rates according to the thickness
reduction in the deepest sector and the deepest point as well as
the weight loss per length unit. For a better comparison of the
influence of the temperature Fig. 5 shows the rate in the dee-
pest point versus the metal temperature. The wall thickness of
unexposed tubes of X20 was uneven since the inner and outer
diameters were eccentric. This complicated the evaluation of
the thickness reduction. Therefore, the data for the tubes kept
at 478 8C and 534 8C is only indicative. Only the weight loss is
shown for the tube at 510 8C. The thickness data for Alloy
304L are somewhat uncertain for similar reasons.
The corrosion attack of the individual alloys will be pre-
sented below but first some general trends will be pointed

Fig. 4. The corrosion rates for all test

tubes according to the thickness reduction
in the deepest sector and the deepest point
as well as the weight loss per length unit
Materials and Corrosion 2005, 56, No. 7 Superheater corrosion in a CFB waste boiler 453

Fig. 5. The corrosion rate in the deepest point versus temperature

Fig. 7. The average thickness reduction around tubes of alloy T22.
The highest deposit crests were located at the top
out. The weight loss data gives a reliable measure of the av-
erage thickness loss on the entire tube surface. However, it is
The average corrosion depths in the 12 sectors around the
not very useful to estimate the tube lifetime. The occurrence of
tube periphery are shown in Fig. 7 for all test tubes of alloy
a few deep pits will not be reflected in the weight loss. Since
T22. The diagrams have been rotated so that the estimated
the weight loss also shows similar trends as the thickness re-
direction of the highest deposit crest is upwards for all tubes.
duction it will not be further discussed, except for alloy X20.
It is seen that the tube at 516 8C was attacked all around the
The difference between the deepest point and the deepest sec-
tube, but most at approximately
908 from the crest. The av-
tor is an indicator of the tube roughness. A large difference
erage corrosion of the tube at 502 8C was less severe, but in
may occur when a pitting attack took place on the tube, as
pits away from the deposits the thickness was still reduced
for e.g. the austenitic steel Alloy 310.
with up to 2 mm. For all other test tubes the pits were concen-
The temperature dependence of the ferritic steel T22 shows
trated to a band at the edge of the deposit, typically 30 – 608
a clear bell shaped form with a maximum attack at 515 8C.
from the crest. That was also the location of the deepest sec-
Despite that the decrease at high temperature was less pro-
tors.
nounced, also the corrosion rate of the Ni rich austenitic steel
Alloy 28 was slightly bell-shaped. For the Ni-based alloy Al-
loy 65 the highest corrosion rate actually occurred at the low-
3.2.3 The martensitic steel X20, full name X20CrMoV121
est temperature. All other alloys had rates that increased with
(Fe10Cr1Mo)
the temperature.
The corrosion of alloy X20 was quite severe not only under
the deposits and at the edges of them, but also on the sides of
3.2.2 The ferritic steel T22 (Fe2Cr1Mo)
the tubes. It was only on the leeward side that the corrosion
was slower and the pitting less severe. Both the overall corro-
The most striking with this alloy is the dramatic attack at
sion rate and the general pitting attack increased substantially
516 8C. The deepest point was 2.9 mm under the original me-
with the temperature, but there were a few deep pits formed
tal surface. Only 1.6 mm remained. Fig. 6 shows a photo of
already at 478 8C. The pits that were formed did not have the
this tube after water-jet cleaning. The deposit crest had
same shape as those on alloy T22. They were smaller, typi-
been about in the middle of this view. Large interconnected
cally 1 mm in size, with sharper edges between them (c.f.
pits are seen towards the sides. The appearance is that of
Fig. 8). Apart from the pits the surface was rougher or
hot corrosion attack.
wavy, especially at the highest temperature. It was noticed
that the oxide was darker and more adherent than on any other

Fig. 6. The water-jet cleaned surface of T22 at 516 8C. The deposit Fig. 8. The water-jet cleaned surface of X20 at 534 8C. The deposit
crest was located in the center crest was located in the centre
454 Andersson and Norell
Fig. 9. The average thickness reduction around tubes of Alloy
304L. The highest deposit crests were located at the top
alloy. The oxide was not completely removed by the water-jet
cleaning. Since the unexposed tube had uneven wall thickness
no diagram with thickness reduction around the tubes is
shown.
3.2.4 The austenitic steel Alloy 304L (Fe18Cr10Ni)
The attack of 304L was correlated to the deposit crest. This
can be clearly seen for the tube at 536 8C in Fig. 9. The thick-
ness reductions in the sectors at both 3008 and 30 – 908 are
deeper than at 3308. This corresponds to an attack that is dee-
per at the edges of the deposit than right under its crest. Also
the tubes at 478 8C and 510 8C have corroded more on the edge
of the deposit than under the crest. Though this only occurred
on one side at these temperatures, it should be remembered
that the flue gas flow was not symmetric around the test tubes.
The general corrosion of this alloy increased with the tem-
perature. On the other hand, the pitting was less pronounced
than on the ferritic/martensitic steels and also less temperature
dependant.
Fig. 10. The water-jet cleaned surface of Alloy 310 at 508 8C. The
pits are located at 308 on the side of where the deposit crest was
located
Materials and Corrosion 2005, 56, No. 7
Fig. 11. The average thickness reduction around tubes of Alloy
310. The highest deposit crests were located at the top
3.2.5 The austenitic steel Alloy 310 (Fe25Cr21Ni)
This alloy suffered from severe pitting in a manner different
from all other alloys in the test. The pits were formed at all
temperatures following a narrow line about 308 from the de-
posit crest, c.f. Fig. 10. The number and size of the pits in-
creased with increasing temperature. At the two higher tem-
peratures the pits actually penetrated the outer alloy down to
the ferritic core of this composite tube. The core was made in
the ferritic steel T22. At the interface to the core tube the pits
had flattened and spread a bit along the interface. In fact, it
appears as if their growth in depth almost stopped at the inter-
face. Few pits were actually deeper than the thickness of the
outer alloy. This can also explain why the deepest points were
almost equally deep at 508 8C and 532 8C. The pitting attack
was observed mainly on one side of the deposit, a conse-
quence of the top coil and the resulting difference in gas
flow, c.f. Fig. 11. The general corrosion rate increased with
the temperature, but in view of the pitting attack this is of mi-
nor importance.
Fig. 12. The average thickness reduction around tubes of Alloy 28.
The highest deposit crests were located at the top
Materials and Corrosion 2005, 56, No. 7
Fig. 13. The average thickness reduction around tubes of Alloy
825. The highest deposit crests were located at the top
3.2.6 The high-alloyed austenitic steel Alloy 28
(Fe27Cr30Ni3Mo)
This was the least corroded alloy in the test both at the low-
est and highest test temperatures. The deepest point that was
found after one month at 462 8C was about 0.14 mm deep. The
corrosion was too moderate to establish its angular depend-
ence at this temperature. No signs of pitting were seen.
The corrosion rate had a somewhat bell-shaped temperature
dependence and was considerably higher at 504 8C. The alloy
was slightly preferentially attacked 308 from the deposit crest
at both 504 8C and 528 8C, c.f. Fig. 12. The corroded surface
was also rougher in these sectors as compared to under the
crest, but no actual pits were observed.
Fig. 14. The average thickness reduction around tubes of Alloy 65.
The highest deposit crests were located at the top
Superheater corrosion in a CFB waste boiler 455
Fig. 15. Detail of the water-jet cleaned surface of Alloy 65 at
474 8C. Half the tube diameter is shown. Pits are seen that occurred
on the side of the deposit crest
3.2.7 The nickel-iron-based Alloy 825 (39Ni31Fe22Cr3Mo)
Also Alloy 825 corroded comparatively little in this test,
though the rates were substantial and increased with the tem-
perature. It was the least corroded alloy at the middle tempera-
ture. Moreover, there were signs of pitting. As seen in Fig. 13
the attack was actually quite uniform, somewhat like for Alloy
28. The deepest sectors were found at the edges of the deposit
crests, but they were not much deeper than under the crest.
Also, the leeward side of the tubes were attacked to almost
similar extent.
3.2.8 The nickel-based alloy Alloy 65 (61Ni21Cr9Fe 8Mo)
The attack of Alloy 65 was different from that on other al-
loys in two ways. First, the corrosion rate decreased with the
temperature. At the lowest temperature the attack of Alloy 65
was substantially faster than that of the other high-alloyed ma-
terials in the test, Alloy 28 and Alloy 825, at their lowest tem-
peratures. At higher temperatures these three alloys performed
rather equal. Secondly, the most severe corrosion occurred
right under the deposit crest and not at the edge of it as
seen in Fig. 14. Furthermore, at the lowest temperature
some pitting was observed at the edge of the severely corroded
region, towards the side of the deposits, c.f. Fig. 15. Also un-
der the deposit crest the corroded surface was rough as from
pitting. Even though no distinct pits were observed on the high
temperature tubes, visual inspections indicated that similar
corrosion mechanisms took place at all temperatures.
4 Discussion
The high metal temperatures and the location of the coil
accelerated the corrosion rates in this field test. The corrosion
attacks therefore were very severe. On the most corroded tube
of the ferritic steel T22 the remaining goods in the deepest pit
was only 1.6 mm thick. Moreover, also some test tubes of the
high-alloyed materials had almost equally high corrosion
rates. Similar rates have been reported previously in waste
combustion under similar conditions [2]. The corrosion of
the different alloys will be compared and discussed below,
but first some factors that might have caused this severe cor-
rosion will be considered.
456 Andersson and Norell
First of all it should be remembered that the test was in-
tended to examine the corrosion at high temperatures for fu-
ture applications. Therefore, the outgoing steam temperature
from the test coil was more than 200 8C higher than the steam
produced during ordinary operation in this boiler. It is also
known that the corrosion rate in waste combustion decreases
with decreasing flue gas temperature [21, 22]. The test coil
was installed after the upper draw. In later boiler designs
the superheaters are placed further away from the cyclones
where the flue gas temperature is lower. Unfortunately, no
thermocouple was available to measure the flue gas tempera-
ture close to the test coil so the parameter is not known for this
test. Concerning the boiler, it should also be kept in mind that
it usually burns a fuel with 60% RDF and not 100% as it was
during the test. The increased metal temperature and the fuel
composition were intentional choices to create a severely cor-
rosive environment for the test.
The severe corrosion in waste combustion is often attribu-
ted to the presence of Zn and Pb in the deposits [4 – 8]. These
may contribute to the formation of eutectic chloride melts
with low melting points. However, it is unlikely that such a
mechanism played an important role in this test. Only minor
amounts of these elements were encountered in the deposits.
The analyses of the deposits and scales will be further treated
in part two of this paper.
The flue gas flow was not perpendicular to the test coil,
which resulted in the formation of two deposit crests on
many tubes. It can also be expected that the flow rate and con-
sequently the flue gas impact were more severe on one side of
the tube. It has been shown that the corrosion rate increases
with the flue gas flow rate [14]. Thus, the flue gas flow pattern
can explain that the preferential attacks were mainly observed
on one side of the deposit crest.
Most alloys were preferentially attacked at the edges of the
deposit crest. The most obvious example was the austenitic
steel Alloy 310 with pits restricted to a narrow band where
severe corrosion occurred. The reason for this is not known,
but it is clear that a very specific combination of conditions
have triggered the mechanism. There were only two excep-
tions. First, at the two middle temperatures the severely cor-
roded tubes of the ferritic steel T22 were preferentially at-
tacked further away from the deposit crest at
908. Secondly,
Alloy 65 was preferentially attacked right under the deposit
crest. The preferential attack at the edge of the deposit has
previously been observed on tubes of Alloy 28 that had
been exposed for 5400 h at 340 8C in a waste boiler [4]. Similar
observations have been reported for Alloy 310 [14]. Deposit
induced corrosion is a complex corrosion mechanism but it
involves several reactions between alkali chlorides, sulphates,
H2O, O2, Cl2, HCl, metal chlorides and oxides in different
layers of the scale and deposits [23]. The suggested mechan-
isms rely on the existence of these layers, different activities
for the reactants within them and the transport between them. It
is therefore not surprising if rapid corrosion occurs where these
layers exist but still are thin. Laboratory exposures with cou-
pons of Alloy 310 and Alloy 28 embedded in KCl-tablets have
shown that the most severe attack can occur at a critical deposit
thickness that was 1 – 2 mm in that study [24].
Comparing the corrosion rates, c.f. Figs. 4 and 5, it is seen
that the alloys with the best overall corrosion resistance were
the high-alloyed austenitic steel Alloy 28 and the nickel-based
Alloy 825. At the lowest temperature the ferritic steel T22 ac-
tually performed quite well whereas the nickel-based Alloy 65
was about equally resistant as Alloy 28 and Alloy 825 at me-
dium and high temperatures. In Fig. 4 the alloys are ordered
Materials and Corrosion 2005, 56, No. 7
with increasing CrþNiþMo content from left to right. It is
clear that a major step in corrosion resistance prevails between
the austenitic steel Alloy 310 and Alloy 28. These two alloys
are both austenitic with about equal Cr-contents but Alloy 28
contains about 10 wt-% more Ni (30.4 vs. 21.1) and 3.3 wt-%
Mo versus 0.1% for Alloy 310. The highest corrosion rates
occurred on the ferritic and martensitic steels. Nevertheless,
considering their higher alloying content the severe pitting of
Alloy 310 and the corrosion of Alloy 65 at the lowest tempera-
ture were less expected.
The corrosion rates generally increased with the tempera-
ture though in some cases the corrosion decreased with in-
creasing temperature. For the ferritic steel T22 there was a
maximum in the corrosion rate at the two middle tempera-
tures. The thickness reductions also differed. At the highest
and lowest temperatures the most severe attack occurred at
the edge of the deposit crests, but at the middle temperatures
the deepest sectors were found further away from the crests.
This suggests that a different corrosion mechanism has oc-
curred at the middle temperatures. When the deposit thick-
ness, c.f. Fig. 3, is compared to the corrosion rates it is
seen that thinner deposits are formed on T22 at the middle
temperatures were the highest corrosion rates occurred.
This is an interesting observation since it is obvious that
the corrosion rates relate to the deposit thickness for all alloys.
A closer comparison of the ferritic steel T22 and the mar-
tensitic steel X20 shows that the corrosion rates were higher
for the martensitic steel at the higher and lower temperatures,
despite its higher Cr-content. However, also laboratory experi-
ments simulating Cl-containing combustion gases have shown
that X20 can corrode faster than T22 at 450 8C [25]. Other
experiments have shown that nickel free iron-chromium al-
loys do not form protective Cr2O3 in waste combustion atmo-
spheres but mixed oxides corresponding to the alloy composi-
tion [26].
In the literature it is often stated that nickel-based alloys
with about 60 wt-% Ni and 8 – 18 wt-% Mo are the most sui-
table in waste boilers if the environment is severely corrosive
[17, 27]. Although Alloy 65 has a composition within this ran-
ge, it did not perform well at the lowest temperature, 474 8C,
where it actually had the highest corrosion rate of all alloys.
However, it has been observed that the addition of nickel,
chromium, and molybdenum can increase the corrosion resist-
ance significantly in waste boilers at 550 8C but that alloying
content may be less important at 450 8C [15]. Generally, over
the examined temperature range the corrosion resistance in-
creased with the alloying content. However, the corrosion be-
haviour of Alloy 65 was different from that of the other alloys.
Its corrosion rate decreased with the temperature and the
thickness reduction was highest directly under the deposit
crest. This indicates that the most severe corrosion of this al-
loy occurs under other conditions than for the other alloys.
Deposit induced corrosion, where the deposit is providing
chlorine gas to the metal surface, is still a possible mechanism.
However, directly under the deposit crest the oxygen activity
can be lower than under thinner deposits. Thus, protective oxi-
des will form less easily.
The high-alloyed austenitic steel Alloy 28 had a slightly
decreased corrosion rate at the highest temperature. Such de-
creasing corrosion rates for high-alloyed austenitic steels and
nickel-based alloys in waste incinerator systems have been
reported previously, though that was for the Alloys 310 and
Alloy 825 [2]. The effect was attributed to the formation of
thicker and more protective oxides at higher temperatures.
Materials and Corrosion 2005, 56, No. 7
The pitting attack observed on Alloy 310 was obstructed at
the inner tube where it spread out under the outer alloy. This
implies that the composite structure has protected the tubes
from being penetrated by pitting corrosion.
The size of the test coil allows for a thorough evaluation of
the corrosion of the test tubes. Nevertheless, due to the size of
the coil it needs to be considered whether the corrosive envir-
onment differed between the test tube positions. In practice, it
is barely impossible to answer that question. Instead, the dis-
tribution of the corrosion rates across the test coil can be as-
sessed in relation to some striking results. The nickel-based
alloy Alloy 65 corroded more than any other alloy at the low-
est temperatures. It could be argued that this was related to e.g.
variations in the flue gas flow pattern. The tube was positioned
next to the quarter of the coil where the deposit formation was
limited. Nevertheless, the other alloys tested in the same area
were less attacked. Another observation concerns the bell-
shaped corrosion of the steel T22. The two most corroded
tubes of this alloy were also positioned in the vicinity of
the quarter with limited deposit formation. Yet in the same
manner, positioned next to the most corroded tube, at
516 8C, was the tube of the nickel-based Alloy 825 that
was the least corroded at this temperature. A final example
is that the corrosion rates of the austenitic steel Alloy 310
and the nickel-based Alloy 65 showed opposite temperature
dependencies. Still, these tubes were consistently positioned
next to each other so the result can hardly be related to differ-
ing corrosive conditions across the test coil. The possible in-
fluence of the flue gas flow pattern on the corrosion rate can
never be entirely ruled out. However, it is concluded that the
test tube temperature was the most important factor affecting
the corrosion rate of the test tubes.
In this part one of the paper the corrosion rates for waste
boiler candidate materials have been examined. The metal
loss have been characterised and related to the metal tempera-
ture, the alloy composition and the deposit crest. In part two of
the paper a detailed study of the reaction products will be pre-
sented. The focus will be on the metal oxides that were formed
and the inner part of the deposits that were interacting with the
alloy and the oxide during the field test. The aim will be to
study the corrosion mechanisms more in detail and identify
factors that determined the performance of the alloys. Four
of the alloys that were tested in the field test have been se-
lected for this study, based primarily on their performance
in the field test. The ferritic steel T22 was partly chosen as
a reference because it is a common alloy in many boilers.
The austenitic steels Alloy 310 and Alloy 28 were chosen
for their difference in corrosion behaviour where Alloy 310
was severely attacked by pitting corrosion, unlike Alloy 28.
The nickel-based Alloy 65 was chosen since the corrosion at-
tack was significantly different from the other alloys.
5 Conclusions
l The corrosion rates were accelerated due to increased metal
temperature and the location of the tube coil near the cy-
clone. The highest corrosion rate on T22 was 34 mm/
year. Also some test tubes of high-alloyed materials had al-
most equally high corrosion rates.
l The flow pattern of the gas highly influenced the deposit
build up and the corrosion attack. However, local variations
along the test coil seemed to be of less importance for the
corrosion than the metal temperature.
Superheater corrosion in a CFB waste boiler 457
l The deposit amount was alloy dependent. The low-alloyed
steels formed thick deposits at all temperatures while this
thickness increased with the temperature on the high-al-
loyed austenitic steels and the nickel-based alloy.
l The alloys, except Alloy 65, were preferentially attacked at
the edge of the deposit crest.
l Alloy 28 and Alloy 825 had the best overall corrosion re-
sistance over the temperature range of all alloys in the test.
The attack on both alloys was uniform and no pitting was
observed.
l The corrosion rate on the ferritic steel T22 was bell-shaped
with the highest rate at 516 8C. At 460 8C was the corrosion
rate of the same order as for the more alloyed steels and
lower than for the nickel-based alloy Alloy 65. The fastest
attack took place at
908 angle from the deposit crest.
l The austenitic steel Alloy 310 was severely attacked by pit-
ting in a narrow band along the edge of the deposits.
l The corrosion on the nickel-based alloy Alloy 65 differed
significantly from the other alloy. The attack was preferen-
tial under the deposit crest. Furthermore, the corrosion rate
decreased with increasing temperature.
6 Acknowledgements
The Swedish High-Temperature Corrosion Centre at Chal-
mers University of Technology is acknowledged for financial
support. Kvaerner Power and AB Sandvik Steel are acknowl-
edged for a fruitful cooperation.
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(Received: December 13, 2004) W 3852