UPDATE ON THE FIRESIDE CORROSION

RESISTANCE OF PROPOSED ADVANCED

ULTRASUPERCRITICAL SUPERHEATER AND
REHEATER MATERIALS: LABORATORY
AND FIELD TEST RESULTS

Michael S. Gagliano, Horst Hack and Greg Stanko

Foster Wheeler North America Corp.
Livingston, NJ 07039

Presented at:
The 2009 Clearwater Coal Conference
34th International Technical Conference on Coal Utilization & Fuel Systems
Clearwater, FL
USA
May 31 – June 4
 UPDATE ON THE FIRESIDE CORROSION RESISTANCE OF PROPOSED
ADVANCED ULTRASUPERCRITICAL SUPERHEATER AND REHEATER
MATERIALS: LABORATORY AND FIELD TEST RESULTS

Michael Gagliano (michael_gagliano@fwc.com; Tel. 973-535-2322; Fax. 973-535-2242)

Horst Hack (horst_hack@fwc.com; Tel. 973-535-2200; Fax. 973-535-2242)
Greg Stanko (greg_stanko@fwc.com Tel. 973-535-2256; Fax. 973-535-2242)

Foster Wheeler North America Corp.

12 Peach Tree Hill Rd
Livingston, NJ 07039

Abstract
In an effort to reduce emissions of CO 2 and other harmful pollutants from coal-fired power plants, the
power generating industry is moving towards the use of advanced, ultra-supercritical steam cycles, with
steam temperature approaching 760°C (1400°F) and operating pressures of 35 MPa (5000 psi). Since
boiler materials used in conventional power plants do not possess the requisite high temperature
mechanical properties and corrosion/oxidation resistance to meet these requirements, the US Department
of Energy (DOE) and the Ohio Coal Development Office (OCDO) are co-sponsoring a multi-year project,
which is managed by Energy Industries of Ohio (EIO), to thoroughly evaluate promising materials. As
part of this project, which was co-funded by Foster Wheeler North America Corp., several materials,
including high-strength austenitic stainless steels, nickel-based alloys, diffusion coatings and weld
overlays have been evaluated for fireside corrosion resistance through laboratory and field tests. This
paper provides an update on field testing progress, and a comparison of the laboratory test results with the
field test results after one and two years of exposure to Midwestern (high-sulfur bituminous) and Western
(low-sulfur, powder river basin) coal conditions.

INTRODUCTION
Due to its availability, reliability and affordability, coal is extensively used as a primary fuel source for
electric power generation both in the United Stated and throughout much of the world. Coal combustion
can result in emissions of higher levels of greenhouse gases and other pollutants per unit energy than
other fuels, which when coupled with increasingly more stringent air quality regulations, poses a unique
set of challenges for the coal’s continued use as a major fuel source. Since the cycle efficiency of a coal-
fired power plant is directly influenced by steam temperature and pressure, incorporation of advanced
ultrasupercritical (A-USC) steam cycles promises not only to improve cycle efficiency, but also
significantly reduce green house gas emissions.
Current worldwide research and development efforts are focused on enabling the construction of
ultrasupercritical plants operating with steam temperatures as high as 760ºC (1400ºF) and steam pressures
in excess of 35 MPa (5000 psi), as such conditions can potentially increase cycle efficiencies to greater
than 47% percent HHV and reduce CO 2 emissions by almost 25%. Even more significant reductions in
CO 2 emissions can be achieved by the integration of oxycombustion technology with A-USC steam
cycles. In the United States, advanced materials research is being undertaken by a consortium of boiler
and turbine manufactures, and Oak Ridge National Laboratories. For the last six years, the extensive
research and development program, which is co-funded by the United States Department of Energy
through the National Energy Technology Laboratory (NETL) and the Ohio Coal Development Office
(OCDO), managed by Energy Industries of Ohio (EIO) and under the technical direction of the Electric
Power Research Institute (EPRI) has been aimed at evaluating the high temperature mechanical properties
and oxidation/corrosion behavior of advanced alloy systems, and developing fabrication practices for use
of these materials in an A-USC plant.

Fireside Corrosion
In coal-fired boilers, especially those burning high sulfur coals, severe fireside wastage of superheater and
reheater tube surfaces is generally caused by coal ash corrosion resulting from the formation of molten
alkali iron trisulfates.(2-6) Within the heat recovery areas, as alkali sulfate deposits build up on tube
surfaces, the outermost material becomes sticky and captures fly ash particles. Breakdown and
subsequent catalysis of sulfur compounds in the fly ash produces SO 3 , which reacts with iron oxide and
alkali sulfates in the deposits to form relatively low melting temperature alkali-iron trisulfates at the metal
interface. Once formed, these molten alkali iron trisulfates flux the protective oxides from the metal
surface, thereby leading to accelerated oxidation and sulfidation of the underlying metal. Corrosive losses
resulting from coal ash corrosion generally increase very rapidly as temperatures exceed about 595ºC
(1100ºF) then drop-off with increasing temperatures greater than 735ºC (1350ºF). Thus, as operating
steam temperatures (and corresponding metal temperatures) are continually increased, severe metal loss
resulting from coal ash corrosion is expected to remain a critical concern that must be resolved before A-
USC plants can be successfully deployed.
As a precursor to the current research, extensive laboratory and field testing programs sponsored by the
EPRI, Foster Wheeler Development Corporation, and Ishikawajima Harima Heavy Industries Co, Inc.
explored the influence of metal temperatures, alkali levels and SO 2 concentrations on coal ash
corrosion.(7-8) Laboratory testing of several wrought superheater/reheater alloys and coatings indicated
that metal wastage generally increased with increasing concentrations of SO 2 and alkali sulfates, and the
influence of temperature generally followed a bell-shaped curve that shifted and varied in width with
changes in alloy composition, SO 2 level, alkali content, and CaO concentration.(7) The study also
confirmed that a material’s resistance to coal ash corrosion is primarily dependent on chromium content
with alloys containing greater than 22% chromium generally exhibiting satisfactory corrosion resistance.
Subsequent field testing was performed by mounting tubular coupon specimens onto air-cooled corrosion
probes and installing the probes into three host boilers; two burning relatively aggressive Eastern
bituminous coal, the other a burning a seemingly non-corrosive low-sulfur Western sub-bituminous coal.
The test specimens were maintained at metal temperatures between 650°C and 700°C (~1200°F and
1300°F) and exposed for up to 16,000 hours. Post exposure analysis of the coupon specimens indicated
that while the degree of metal wastage was comparable for all samples removed from all three locations,
the corrosion mechanism was vastly different. Samples exposed to the high-sulfur Eastern bituminous
coal showed wastage morphologies and attack patterns that were typical of coal ash corrosion, while
samples exposed to Western sub-bituminous coal showed similar corrosion morphologies, but the attack
pattern was atypical for coal ash corrosion and more consistent with sulfidation (8). Although the results
from the unit burning Western coal were somewhat unexpected, the field study again showed that
materials containing roughly 25% chromium exhibited satisfactory resistance, regardless of the fireside
corrosion mechanism.
With the US DOE’s target conditions for advanced ultrasupercritical power plants calling for maximum
steam temperatures approaching 760°C (1400°F), metal temperatures are likely to exceed 815°C
(1500°F). Even though such metal temperatures are well outside the range where coal ash corrosion is
expected, corrosion can still be problematic for high nickel and nickel-based alloys due to sulfidation and
oxidation reactions. Unfortunately, since conventional coal-fired boilers typically operate with
superheater/reheater metal temperatures in the range of 620°C - 700°C (1150°F - 1300°F), where
advanced austenitic materials are suitable, no field corrosion data exist for most of the high-strength, high
nickel alloys currently proposed for A-USC superheater/reheater tubing.
EXPERIMENTAL PROCEDURE
Table 1: Nominal Compositions of SH/RH Materials
Materials Selection Alloy Composition
A number of prospective wrought advanced 304 70Fe–18Cr–8Ni
Super 304H 68Fe–18Cr–9Ni–3Cu–Nb–N
austenitic stainless steels and nickel-based
347HFG 67Fe–19Cr–11Ni–Nb
alloys, as well as several laser claddings, weld HR3C 53Fe–25Cr–20Ni–Nb–N
overlays and diffusion coatings were selected SAVE 25 50Fe–22Cr–18Ni–3Cu–1.8W–Nb–N
for corrosion evaluation. The initial selection 800HT 45Fe–32Ni–20Cr–Ti–Al
of candidate materials was not only based on HR120 37Ni–35Fe–25Cr–Si–Nb–N
only corrosion resistance, which was based on 353MA 36Fe–35Ni–25Cr–1.5Si–N–Ce
previous laboratory and field tests for HR6W 40Ni–25Fe–23Cr–6W–Nb–Ti–B
advanced-cycle plants (9-10), but also on the 45TM 46Ni–27Cr–23Fe–2.8Si–Ce
material’s high temperature mechanical 214 76Ni–16Cr–4.5Al–3.5Fe
properties, oxidation resistance, availability, 602CA 63Ni–25Cr–10Fe–2.3Al–Zr–Y
230 60Ni–22Cr–14W–1.5Mo–Fe–Al–B
weldability, and fabricability(1). Furthermore,
740 50Ni–25Cr–20Co–5Mo–2Nb–2Ti–Al
since corrosion behavior was evaluated under Nimonic 263 51Ni–20Cr–20Co–5.8Mo–2.2Ti–Al –B
various coal conditions, even some alloys 617 54Ni–22Cr–13Co–9Mo–1.5Fe–Al–Ti
containing less than 22% chromium were 622 Overlay 58Ni–21Cr–14Mo–4Fe–3W
assessed as potential candidate materials for 52 Overlay 58Ni–29Cr–10Fe–Al–Ti
units burning less aggressive coals. The 72 Overlay 55Ni–44Cr –Ti
nominal compositions of the wrought
superheater/reheater alloys and as well as the laser clad/weld overlay materials are listed in Table 1.
Diffusion coatings, including straight chromizing (FeCr), AlCr and SiCr, were also evaluated and selected
based on the ability of diffusion coatings to form a strong metallurgical bond, while offering excellent
resistance to high temperature corrosion and oxidation. Diffusion coatings were applied to Super 304H
wrought material and thicknesses generally varied between 150 µm (0.006”) and 250 µm (0.010”).

Laboratory Testing
Fireside corrosion resistance of candidate superheater/reheater materials was evaluated through laboratory
and field testing. Laboratory testing was performed by coating rectangular test coupons with specific
synthetic ash mixtures, vertically suspending the coupons on racks inside sealed, insulated tubular electric
furnaces and passing steady synthetic flue gas streams over the test specimens. The test parameters
(deposit and gas compositions and testing temperatures), which were reported previously(11-12), were
designed to essentially encompass the range of environmental conditions that are may prevail in the
superheater/reheater area of the boiler while burning Midwestern (high sulfur bituminous), Eastern
(medium sulfur bituminous) and Western (low sulfur Powder River Basin) US coals. The total duration
of the corrosion tests were 1000 hours, and testing was carried out at temperatures of 650°C (1200°F),
705°C (1300°F), 760°C (1400°F), 815°C (1500°F), and 870°C (1600°F). After each 100 hour interval,
the corrosion coupons was removed from the furnace, gently cleaned of the spent synthetic ash mixture,
recoated with fresh ash and returned to furnace. This was done to ensure that the coupon surfaces were
constantly kept in contact with active corrosive species for the entire test duration. Following completion
of 1000 hours exposure, the test coupons were examined both macroscopically and microscopically in
order to determine the extent of total metal wastage; the results of these tests have been presented
previously(11 - 12).

Field Testing
Laboratory testing is a valuable screening tool for assessing the corrosion resistance of a number of
different materials exposed to specific synthetic environments for relatively short exposure times;
however there are a number of variables, such as actual (dynamic) deposit compositions; variability in
SO 3 concentration; temperature fluctuations in the ash and flue gas, and on the tube surfaces; fly-ash and
flue gas movement across the tube surfaces; sootblowing operations and/or deslagging; etc., that can only
be tested through field testing. Thus, field corrosion tests were conducted, not only to validate
conclusions that were drawn under laboratory test conditions, but also to evaluate some of the more
critical parameters that could not be accounted for under laboratory testing conditions.
Field testing was performed by inserting two air-cooled, retractable corrosion probes into the superheater
or reheater sections of three host utility boilers. The probes were designed to be completely independent
of the main boiler, easily inserted and removed without requiring an outage, and fail safe such that in the
event of power, computer or thermocouple failure, or loss of cooling air or data signal, the probe would
automatically retract outside the boiler environment so that testing would not be compromised.
Each probe consisted of thirty (30) material coupons, which were machined into uniform, concentric
tubular test specimens. Prior to assembly, the wall thickness of each coupon specimen was measured at
eight equally spaced positions (every 45º) around the diameter and recorded, such that the 12 o’clock
position presented the top surface of the probe. The corrosion probes were separated into five zones, each
containing five specimens and one thermocouple element; the thermocouple elements separated adjacent
zones and were used to measure the metal temperature within a given zone. By adjusting the air flow
through the annular space within the probe core, the surface metal temperature could be controlled within
the range anticipated for superheater and reheater components of a USC plant. Thus, each zone was
intended to represent the specific temperature regimes that were tested under laboratory conditions:
650°C (1200°F), 705°C (1300°F), 760°C (1400°F), 815°C (1500°F), and 870°C (1600°F).
Probe host sites were initially selected based upon their primary fuel source, such that field corrosion data
could be generated for each of the three major US coal types: Midwestern, Western, and Eastern. In
January 2006, June 2006 and September 2008 three pairs of corrosion probes were successfully installed
at a Midwestern, Western and Eastern host utility site, respectively. For the duration of the test period,
probe status and temperature data have been continuously monitored and collected remotely. Routine on-
site inspections have also been performed to visually assess the condition of the probes and ensure that
the probe assemblies are operating accordingly. Upon completion of the desired exposure period, the
probe was removed from the host utility site and returned to the Foster Wheeler research facility in
Livingston, NJ for post exposure evaluation, which included visual examination and documentation of
each coupon specimen; wall thickness measurements at appropriate locations around the circumference,
microscopic examination and quantification of subsurface penetration and SEM/EDS analysis of the
deposits and subsurface species, if applicable.
The choice of materials and layout orientation of the different coupons samples on each probe was based
upon knowledge of the fuels being burned at each host site, and the preliminary results of the laboratory
tests. Table 2 presents the specimen layouts for the one and two year probes installed at the Midwestern
and Western host sites. It should be mentioned that while probes have been recently been installed at the
Eastern host site, the prescribed exposure period of at least one calendar year has not been achieved, and
therefore no update on field testing under Eastern coal conditions is currently available.

RESULTS
Laboratory Testing
Results of the maximum measured wastage (TMW) for each test material (wrought and coating/overlay)
are displayed in Figures 1 and 2 after 1000 hours of exposure to temperature between 650ºC and 870ºC
(1200ºF and 1600ºF) for synthetic Midwestern and Western coal conditions, respectively. Since
chromium is essential for providing high temperature corrosion and oxidation resistance, the materials
(except for the chromized coating and 50/50 laser cladding) are arranged along the x-axis in order of
increasing chromium concentration. Comparison of the two bars graphs indicates that under controlled
isothermal test conditions, wastage is strongly influenced by the alloy composition - specifically
chromium concentration, the test temperature and to a great extent, the aggressiveness of the coal.
However, examination of Figure 1 also indicates that exposure to Midwestern coal conditions at
temperatures of 760 ºC and 815ºC (1400 ºF and1500ºF) resulted in higher than expected corrosion losses
for several high chromium materials. The significant increase in metal loss was due to the presence of
relatively high concentrations of molybdenum. Studies (6-7, 13-14) have shown that molybdenum, when
added in concentrations greater than about 1%, drastically reduces the high temperature corrosion
resistance of stainless steels and nickel-based alloys by increasing the acidity of the molten salt resulting
from the fluxing of MoO 3 from the metal surface. Thus, in the presence of aggressive deposits, corrosion
resistance appears to be primarily affected by the chromium and molybdenum concentrations. The
microscopic appearance of alloy 230 and 72WO exposed to Midwestern and Western coal conditions for
1000 hours at 760ºC (1400ºF) and 870ºC (1600ºF) is illustrated in Figure 3.

Table 2: Specimen Layouts for the Corrosion Probes Installed at the Midwestern and Western Host Sites
Host Site Time 650ºC (1200ºF) 705ºC (1300ºF) 760ºC (1400ºF) 815ºC (1500ºF) 870ºC (1600ºF)
800HT HR3C HR6W 740 72WO/230
740 S304H 230 800HT 740
1 YR 617 800HT 740 50/50 LC 52WO/230
347HFG 622WO/230 52WO/230 SiCr/S304H HR6W
High Sulfur, 230 347HFG 800HT 230 50/50LC
Midwestern Coal HR6W 740 50/50 LC 740 50/50LC
HR3C 617 230 HR3C HR6W
2 YR S304H 230 740 72WO/230 52WO/230
33WO/230 50/50 LC SiCr/S304H 52WO/230 HR3C
622WO/230 HR6W 33WO/230 HR6W 72WO/230
740 HR6W 617 50/50LC 50/50 PTA
800HT S304H 800HT HR3C 230
1 YR 617 HR3C 740 SiCr/S304H 740
230 622WO/230 72WO/230 33WO/230 HR6W
(PRB) Low Sulfur, 50/50 LC 52WO/230 347HFG FeCr/S304H HR3C
Western Coal HR6W 740 617 740 72WO/230
HR3C 617 230 HR3C 740
2 YR S304H 230 740 72WO/230 52WO/230
347HFG 800HT SiCr/S304H 52WO/230 HR6W
622WO/230 347HFG 33WO/230 HR6W 50/50LC

Field Testing
Midwestern Host Site
The one-year field corrosion probe was removed from the Midwestern host site after approximately 5,200
hours of exposure. For the duration of the exposure period, proximate analyses provided by the host site
indicated that the coal contained an average of 3.0% sulfur, 13.2% moisture and 8.8% ash. Upon receipt
to the metallurgical laboratory in Livingston, NJ, the probe surface was covered with relatively thin, hard,
tenacious, brown deposits that were non-uniformly dispersed across the probe length, as shown in
Figure 4a. Following initial inspection and documentation, each coupon specimen was cut into three ring
sections to facilitate macroscopic and microscopic examinations. Visual and microscopic examinations
of the cross-sections revealed very little evidence of corrosion loss on any of the tubular test specimens.
Although some superficial pitting was observed on select samples removed from the intermediate
temperature regions, the extent of pitting was generally negligible as the maximum measured wastage
(defined as the combination of wall loss and subsurface penetration) was determined to be less than 0.13
mm (0.005”).
The second corrosion probe was removed from the host site boiler after approximately 10,400 hours of
exposure. Just prior to removal, a sequence of events caused the probe to experience a short-term high
temperature excursion where probe temperatures briefly exceeded 1100ºC (2012ºF) prompting premature
removal. As a result of the relatively rapid cooling from the higher than expected temperature, the
overwhelming majority of deposits, oxides and/or corrosion products exfoliated from the probe surface.
Thus, upon arrival to the research facility, the probe surface was only partially covered with patchy
deposits and oxides, as illustrated in Figure 4b. Within the intermediate temperature regions, somewhat
thicker patches of tenacious oxides were also apparent at the near 6 o’clock position (bottom).
Total Metal Wastage (in mils/1000 hours)

40
1200°F
650 ºC
35 1300°F
705 ºC
1400°F
760ºC
30
Molybdenum effect
1500°F
815 ºC
870 ºC
1600°F
25

20

15

10

HR3C
HR6W
347HFG

45TM
Nim263
800HT

50/50 LC
622WO

52WO

72WO
602CA

S304H w/FeCr
214

304

Super 304

230

617

740

353

120

S304H w/SiCr
SAVE25

S304H w/AlCr
Material (Arranged in Order of Increasing Cr Content)
Material (Arranged in Increasing Order of Cr Content)

Figure 1: Total Metal Wastage for Coupons Exposed to Synthesized Midwestern Coal Conditions

1200°F
650 ºC
Total Metal Wastage (in mils/1000 hours)

40
1300°F
705 ºC
35 1400°F
760ºC
1500°F
815 ºC
30 1600°F
870 ºC
25

20

15

10

0
HR3C
HR6W
347HFG

45TM
Nim263
800HT

50/50 LC
622WO

52WO

72WO
602CA

S304H w/FeCr
214

304

Super 304

230

617

740

353

120

S304H w/SiCr
SAVE25

S304H w/AlCr

Material (Arranged in Order of Increasing Cr Content)

Material (Arranged in Increasing Order of Cr Content)

Figure 2: Total Metal Wastage for Coupons Exposed to Synthesized Western Coal Conditions
 Midwestern Western

705ºC
(1300ºF)

870ºC
(1600ºF)

Alloy 230 Alloy 230

705ºC
(1300ºF)

870ºC
(1600ºF)

72WO 72WO
Figure 3: Photomicrographs showing the corrosion morphologies on Alloy 230 and 72WO laboratory test specimens
Visual examination of macroscopic cross sections revealed very little evidence of significant wall loss on
any of the probe specimens, except for localized, shallow pitting that was observed at the near 12 o’clock
position (top) of select samples removed from the intermediate temperature regions. Subsequent
microscopic examinations indicated a minor degree of subsurface oxidation and/or sufidation; however,
the degree of penetration was generally very shallow. The total metal wastage observed for every coupon
specimen, irrespective of location or material type/composition was less than 0.26 mm (0.010”).

Western Host Site

The one year corrosion probe installed at host site burning Western coal was removed after nearly 6,300
hours of exposure to boiler operating conditions. Proximate analysis of a representative coal provided by
the host site indicated 0.4% sulfur, 30.8% moisture and 5.4% ash. When the probe arrived in Livingston,
NJ for analysis, the surface was mostly covered with fairly hard, somewhat tenacious, red-orange and
light-colored deposits, as displayed in Figure 5a. Examination of cross-sectional ring specimens revealed
significant wall loss on most of the high nickel, high chromium overlay/cladding material. For the most
part, metal loss occurred indiscriminately around most of the circumference and was not isolated to the
highest temperatures zones. The wrought materials, on the other hand, generally exhibited comparatively
shallower wall loss; however notable wastage was evident on a few wrought specimens located in the
highest temperature regions. Subsequent microscopic and SEM examinations indicated that severe wall
loss on the high nickel, high chromium overlay materials was primarily due to gross subsurface
penetration of oxide and sulfide species.
When the two year probe arrived in Livingston, NJ for metallurgical analysis, the surfaces were covered
with scattered, tenacious light colored deposits, reddish orange deposits and thick, hard black oxide and
corrosion products within the high temperature regions, as shown in Figure 5b. Even without cleaning
the surfaces, considerable metal loss was evident on several of the test specimens which were located near
the probe tip (hottest zone); the most severe ultimately resulting in perforation. Visual inspection of the
cleaned ring sections indicated severe wall loss on most of the overlay/clad materials as well as notable
wastage on several of the wrought alloys, regardless of location along the probe length, although
corrosion tended to increase in severity with increasing effective probe metal temperature. For the
majority of wrought materials, wall loss was localized to discrete sites, whereas on the overlay materials
wall loss was much more general.
The post-exposure surfaces of select specimens removed from the different temperature zones of the
Midwestern and Western probes are displayed in Figures 6 and 7.

(a)

(b)

Figure 4: As received condition of the Midwestern probes after one-year (a) and two-year (b) exposure periods

(a)

(b)

Figure 5: As received condition of the Western probes after one-year (a) and two-year (b) exposure periods
 Midwestern Western

740 Intermediate 740

Temperature
1-year

52WO 72WO

740 Intermediate 740

Temperature
2 -year

33WO 33WO

Figure 6: Photomicrographs of alloy 740 and weld overlay specimens removed from the intermediate temperature
positions on the Midwestern (left) and Western (right) probes after one (top) and two (bottom) calendar years of
exposure. Note the different magnification for the overlay materials removed from the Western probes.
 Midwestern Western

50/50LC Highest 50/50PTA

Temperature
1-year

HR6W HR6W

50/50LC Highest 50/50LC

Temperature
2 -year

HR6W HR6W

Figure 7: Photomicrographs of 50/50LC (PTA) and HR6W specimens removed from the highest temperature
regions on the Midwestern (left) and Western (right) probes after one (top) and two (bottom) calendar years of
exposure. The smaller marker size on the Western probe photomicrographs is indicative of the more severe wastage.
DISCUSSION
Comparison of the laboratory test data presented in Figures 1 and 2 clearly shows that under the
prescribed test conditions, wastage was typically much more severe under simulated Midwestern coal
conditions than for simulated Western coal conditions. Previous studies(7,13,14) have shown that within the
temperature regime where coal-ash corrosion is expected, typically between 1200ºF (650ºC) to 1400ºF
(760ºC), the rate of corrosion is generally driven by the relative amount of SO 2 and O 2 in the flue gas and
the concentration of alkali sulfates (and calcium compounds) in the ash. Thus, the higher concentrations
of alkali sulfates in the Midwestern ash and SO 2 in the flue gas, relative to the Western conditions,
generated greater volumes of molten alkali-iron trisulfates at the metal surface, thereby causing severe
wastage. Corrosion was further limited under synthetic Western condition due to the substitution of all
alkali sulfates with calcium sulfate, a very stable compound that is unlikely to form molten phases under
the prescribed isothermal testing conditions.
In contrast to laboratory testing, field testing showed that severe corrosion may be encountered in the
superheater/reheater areas of advanced ultrasupercirtical boilers when burning seemingly non-aggressive
Western-type (Powder River Basin) coals. Although initial results after one year of exposure suggested
that severe corrosive losses were generally limited to high nickel, high chromium materials that had a
welded microstructure, analysis of the two year probe which had almost 16,000 hours of exposure
indicated that under the appropriate test conditions, perhaps some high nickel, high chromium corrosion
resistant wrought materials may susceptible to relatively high annualized wastage rates. SEM/EDS
analysis of the severely wasted wrought specimens showed corrosion morphologies that were very similar
to overlay materials reported previously(15), where islands of Ni-rich material were surrounded by Cr-rich
oxide and sulfide corrosion products. It should be mentioned, that while several materials (four overlay
and one wrought) exposed to the highest temperatures (where corrosion was most severe) sustained
annualized corrosion rates greater than 1.52 mm/y (60 mpy), two wrought alloys exposed to same
conditions exhibited corrosion rates less than 0.15 mm/y (6 mpy), suggesting that severe wastage was
material specific. Furthermore, previous field testing at the same host site produced relatively high
corrosion rates on several test materials and concluded that wastage was induced by a sulfidation caused
by the formation of CaS(8).

SUMMARY AND CONCLUSIONS

The fireside corrosion resistance of high strength, austenitic stainless steels and nickel-based materials
exposed to Midwestern and Western coal conditions has been evaluated through laboratory and field
testing. While laboratory testing indicated that Midwestern type coal conditions are expected to be cuase
much more severe corrosion under A-USC conditions, field test results suggested that the environment
produced in the superheater/reheater region of units burning Western-type coal may be more corrosive
than originally anticipated, especially for the high nickel, high chromium overlay materials. Although
further analysis of the probes, as well as a detailed investigation into the boiler operating conditions are
required, possible explanations for the gross disparity between laboratory test results and field testing
include:
• Much higher average probe temperatures at the Western site due to operational issues at the
Midwestern site.
• Much shorter exposure period for the Midwestern probes.
• Large temperature fluctuations at the Western site due to soot blowing operations.
• Possible presence of reduced calcium sulfate species at the Western site which were not
accounted for by the isothermal laboratory tests.
ACKNOWLEDGEMENTS
The authors wish to thank Dr. Robert Romanosky and Patricia Rawls (NETL), Robert Purgert (EIO), and
Dr. R. Viswanathan (EPRI) for their support and guidance during this project.
This work was prepared with the support of the U.S. Department of Energy, under Award No. DE-FG26-
01NT41175 and the Ohio Coal Development Office/Ohio Department of Development (OCDO/ODOD) under Grant
Agreement Number CDO/D-00-20. However, any opinions, findings, conclusions, or recommendations expressed
herein are those of the authors and do not necessarily reflect the views of the DOE and/or the OCDO/ODOD".

LEGAL NOTICE/DISCLAIMER
This report was prepared by Foster Wheeler North America Corp. pursuant to a Grant partially funded by the U.S. Department of
Energy (DOE) under Instrument Number DE-FG26-01NT41175 and the Ohio Coal Development Office/Ohio Department of
Development (OCDO/ODOD) under Grant Agreement Number CDO/D-00-20. NO WARRANTY OR REPRESENTATION,
EXPRESS OR IMPLIED, IS MADE WITH RESPECT TO THE ACCURACY, COMPLETENESS, AND/OR USEFULNESS
OF INFORMATION CONTAINED IN THIS REPORT. FURTHER, NO WARRANTY OR REPRESENTATION, EXPRESS
OR IMPLIED, IS MADE THAT THE USE OF ANY INFORMATION, APPARATUS, METHOD, OR PROCESS
DISCLOSED IN THIS REPORT WILL NOT INFRINGE UPON PRIVATELY OWNED RIGHTS. FINALLY, NO
LIABILITY IS ASSUMED WITH RESPECT TO THE USE OF, OR FOR DAMAGES RESULTING FROM THE USE OF,
ANY INFORMATION, APPARATUS, METHOD OR PROCESS DISCLOSED IN THIS REPORT.
Reference herein to any specific commercial product, process, or service by trade name, trademark, manufacturer, or otherwise,
does not necessarily constitute or imply its endorsement, recommendation, or favoring by the Department of Energy and/or the
State of Ohio; nor do the views and opinions of authors expressed herein necessarily state or reflect those of said governmental
entities.

REFERENCES
1. R. Viswananthan, J.F. Henry, J. Tanzosh, G. Stanko, J. Shingledecker, B. Vitalis, R. Purgert. “U.S. Program on Materials
Technology for Ultrasupercritical Coal Power Plants.” Journal of Materials Engineering and Performance. Vol. 14 (3) June
2005. 281 – 292
2. W. Nelson and C. Cain, Jr., "Corrosion of Superheaters and Reheaters of Pulverized Coal Fired Boilers," Transactions of the
ASME, Journal of Engineering for Power, July 1960, pp. 194 - 204.
3. W. T. Reid, "Formation of Alkali Iron Trisulphates and Other Compounds Causing Corrosion in Boilers and Gas Turbines,"
Project Review July 1, 1966, June 30, 1968, prepared by Battelle Memorial Institute, Columbus, OH, June 1968.
4. W. T. Reid, External Corrosion and Deposits: Boilers and Gas Turbines, American Elsevier Publishing Company, New
York, 1974.
5. G. J. Hills, "Corrosion of Metals by Molten Salts," Proceedings of the Marchwood Conference: Mechanism of Corrosion by
Fuel Impurities, Johnson and Littler, eds., Butterworths, London, 1963.
6. S. Kihara, K. Nakagawa, A. Ohtomo, H. Aoki, and S. Ando, "Simulating Test Results for Fireside Corrosion of Superheater
& Reheater Tubes Operating at Advanced Steam Conditions in Coal-Fired Boilers”, High Temperature Corrosion in Energy
Systems, TMS/AIME, M. F. Rothman, ed., 1984, pp. 361-376.
7. W. Wolowodiuk, S. Kihara, and K. Nakagawa, "Laboratory Coal Ash Corrosion Tests," Palo Alto, CA: Electric Power
Research Institute, July 1989. GS6449.
8. J. L. Blough, M. T. Krawchuk, G. J. Stanko, and W. Wolowodiuk, "Superheater Corrosion Field Test Results," Palo Alto,
CA: Electric Power Research Institute, November 1993. TR103438.
9. J.L. Blough, G. J. Stanko, M. T. Krawchuk, “Superheater Corrosion in Ultra-Supercritical Power Plants, Long-Term Field
Exposure at TVA’s Gallatin Station,” Palo Alto, CA: Electric Power Research Institute, February 1999. TR-111239.
10. J. L. Blough, W. W. Seitz, A. Girshik, “Fireside Corrosion Testing of Candidate Superheater Tube Alloys, Coatings, and
Claddings – Phase II Field testing,” Oak Ridge, TN: Oak Ridge National Laboratory, June 1998. ORNL/Sub/93-SM401/02.
11. H. Hack, G. S. Stanko, “Fireside Corrosion Resistance of Advanced Materials for Ultra-Supercritical Coal-Fired
Plants,” 22nd Annual International Pittsburgh Coal Conference, September 2005.
12. H. Hack, G. S. Stanko, “Update on Fireside Corrosion Resistance of Advanced Materials for Ultra-Supercritical
Coal-Fired Power Plants,” The 31st International Technical Conference on Coal Utilization & Fuel Systems,
May 21-25, 2006, Clearwater, Florida, USA.
13. I. M. Rehn, "Fireside Corrosion of Superheater and Reheater Tubes," Palo Alto, CA: Electric Power Research Institute,
1980. CS1653.
14. I. M. Rehn, "Fireside Corrosion of Superheater Alloys for Advanced Cycle Steam Plants," Palo Alto, CA: Electric Power
Research Institute, 1987. EPRI 5195.
15. M.S. Gagliano, H. Hack, G. S. Stanko, “Fireside Corrosion Resistance of Proposed USC Superheater and Reheater
Materials: Laboratory and Field Test Results”, The 33rd International Technical Conference on Coal Utilization & Fuel
Systems, June 1 - 5, 2008, Clearwater, Florida, USA.