Superheater Corrosion in USC Power Plant

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Superheater Corrosion in UltraSupercritical Power Plants

Long-Term Field Exposure at TVA's Gallatin
Station
TR-111239
Final Report, February 1999
EPRI Project Manager

W. T. Bakker
EPRI 3412 Hillview Avenue, Palo Alto, California 94304 PO Box 10412, Palo Alto, California 94303 USA
800.313.3774 650.855.2121 askepri@epri.com www.epri.com
DISCLAIMER OF WARRANTIES AND LIMITATION OF LIABILITIES

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SPONSORED OR COSPONSORED BY THE ELECTRIC POWER RESEARCH INSTITUTE, INC. (EPRI).
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NOR ANY PERSON ACTING ON BEHALF OF ANY OF THEM:
(A) MAKES ANY WARRANTY OR REPRESENTATION WHATSOEVER, EXPRESS OR IMPLIED, (I) WITH
RESPECT TO THE USE OF ANY INFORMATION, APPARATUS, METHOD, PROCESS, OR SIMILAR ITEM
DISCLOSED IN THIS REPORT, INCLUDING MERCHANTABILITY AND FITNESS FOR A PARTICULAR
PURPOSE, OR (II) THAT SUCH USE DOES NOT INFRINGE ON OR INTERFERE WITH PRIVATELY OWNED
RIGHTS, INCLUDING ANY PARTY'S INTELLECTUAL PROPERTY, OR (III) THAT THIS REPORT IS
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REPORT OR ANY INFORMATION, APPARATUS, METHOD, PROCESS, OR SIMILAR ITEM DISCLOSED IN
THIS REPORT.
ORGANIZATION(S) THAT PREPARED THIS REPORT
Foster Wheeler Development Corporation
ORDERING INFORMATION
Requests for copies of this report should be directed to the EPRI Distribution Center, 207 Coggins Drive, P.O. Box
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Copyright 1999 Electric Power Research Institute, Inc. All rights reserved.
CITATIONS
This report was prepared by
Foster Wheeler Development Corporation
12 Peach Tree Hill Road
Livingston, New Jersey 07039
Principal Investigators
J. L. Blough
G. J. Stanko
M. T. Krawchuk
This report describes research sponsored by EPRI.
The report is a corporate document that should be cited in the literature in the
following manner:
Superheater Corrosion in Ultra-Supercritical Power Plants: Long-Term Field Exposure at
TVA's Gallatin Station, EPRI, Palo Alto, CA,: 1999. TR-111239.
iii
REPORT SUMMARY
An advanced, high-strength stainless steel containing 25% Cr performed well in most
areas of a reheater in a boiler fueled with corrosive coals. However, in limited areas it
and all other alloys tested experienced high corrosion rates.
Background
Superheaters and reheaters of coal-fired boilers can fail prematurely due to corrosion
by molten alkali iron sulfates. Such corrosion is generally associated with high-sulfur
coals containing small quantities of volatile alkali compounds and/or chlorine. The
potential for molten sulfate corrosion is greatest in the 1100-1300F (600-700C) range.
EPRI is studying superheater corrosion as part of its program to advance the
technology of advanced, high-efficiency boilers. These boilers will have steam
temperatures in the 1100-1200F (600-650C) range, which brings the tube metal
temperature into the range where corrosion is likely. Prior to the work reported here,
EPRI conducted field trials with air-cooled probes in three plants in the United States
(TR-103438) and one in the United Kingdom (TR-101729). Results from these tests
indicated that corrosion is, indeed, a problem with standard superheater steels such as
SS304, but that alloys or claddings containing 25% Cr or more generally exhibit
acceptable corrosion rates (<4 mils/0.1mm/yr). In this study, spools or sleeves of
promising alloys where built in the reheater of boiler #2 at the Gallatin station of TVA
in various locations and exposed for 35,000-45,000 hours to validate previous results.
Objectives
To study superheater corrosion at temperatures used in ultra supercritical (USC) boilers
as a function of boiler location.
Approach
The research team installed sleeves or spools of seven advanced superheater alloys at
three locations in the reheater of boiler #2 at TVAs Gallatin station. They installed
sleeves in the inlet section of the reheater, where tube temperatures are low. Sleeve
temperature was regulated by the air gap between the sleeve and the tube and
measured by thermocouples. The team built spools of the same alloys into the reheater
in places where the nominal steam temperature was about 1025F (550C). To boost
tube temperature above 1100F (600C), the team built flow-restriction orifices into the
circuits containing the experimental alloys.
v
Sleeves installed near the reheater inlet were removed after approximately 45,000 hours
exposure. Spools installed in the middle of the reheater were removed after
approximately 35,000 hours. Spools installed towards the outlet of the superheater are
still in service (they had very low corrosion rates). After service, the research team
measured corrosion rates and evaluated corrosion mechanisms using standard optical
and scanning electron microscopy.
Results
Corrosion rates observed on all alloys were mainly dependent on boiler location. In
areas shielded from direct impact by fly ash containing flue gas, corrosion rates of
all alloys were low, including corrosion prone alloys such as SS304. In most areas,
the test confirmed previous studies indicating that SS304 type alloys are less
suitable, but that alloys with 25% Cr or more are adequate. In a few isolated areas,
corrosion was so severe that none of the alloys exposed had low corrosion rates.
All alloys exposed showed signs of carburization. This was probably caused by
installation and subsequent use of low-NOx burners in 1994. However, comparison
of corrosion rates of similar alloys before and after installation of low-NO x burners
did not show significant differences in corrosion rates.
EPRI Perspective
This is the final report on the evaluation and qualification of superheater materials for
advanced ultra supercritical boilers. The study included laboratory tests (CS-5195, GS6449), field tests using air-cooled probes (TR-103438, TR-101729), and the full-scale field
test reported here, where the test alloys were an integral part of the steam generator.
From all the data, it is concluded that superheater corrosion will not be a show
stopper for the use of USC boilers. However, for certain coals, steels with a higher Cr
content than the usual 18-8 alloys will be required. In limited areas, additional
protection by shielding or use of 50Cr weld overlays also may be required.
TR-111239
Interest Categories
Fossil steam plant O&M cost reduction
State-of-the-art power plants
Fossil steam plant performance optimization
Keywords
Superheaters
Reheaters
Ultra supercritical boilers
Fireside corrosion
Austenitic stainless steel
vi
EPRI Licensed Material
ABSTRACT
Coal-ash corrosion is a problem that has been plaguing the coal-fired boiler industry
for half a century. This report provides corrosion data for multiple alloys exposed as
reheater tubing for up to 45,000 hours in an actual coal fired boiler. The alloys tested
include 304, 347, 800H, NF-709, HR-3C, CR30A and chromized T-22. They were
exposed to temperature of 604-632 C (1119-1171 F) which is close to the expected
tube-metal temperatures in an advanced ultra-supercritical power plant. The firing
included the use of both conventional and low NOx burners.
The tube wastage was mainly in the form of metal loss at the 2 and 10 oclock position,
and attributed to corrosion/erosion by fly ash-laden flue gas. The tube surfaces were
also usually pitted, and potassium iron-trisulfate was identified as the corrodent.
Internal sulfidation and carburization accompanied the metal loss. The carburization
was caused by carbon deposited during the low NOx firing.
The corrosion rate was found to be dependant on the chromium content in the alloy,
tube metal temperature and the sample location in the reheater. Alloys with chromium
levels over 25 percent had improved corrosion resistance. The corrosion rate as a
function of temperature followed the previous established bell shaped curve. The
wastage increased as the temperature rose in the range of 600-700 C (1112-1292 F)
where the molten alkali-iron-trisulfates are stable. At higher metal temperatures the
alkali-iron-trisulfates dissassociate and the corrosion rate decreases. The exact
parameters governing the aggressiveness of the location are not known but are believed
to include the velocity and temperature of the flue gas, the heat flux, and the ash
deposition rate.
The corrosion rate information is provided at many conditions for the seven alloys
tested. HR-3C was found to provide adequate corrosion resistance for many areas of
the reheater. However, in a limited number of zones, none of the alloys tested will
have adequate corrosion resistance. Tube shields or the use of 40-50 percent chromium
weld overlays may be needed at these locations. Because the number of highly
corroded areas was limited, it is believed that for most boilers and most fuels, the
results of this program provide sufficient data to select superheater and reheater alloys
for ultra-supercritical power plants.
vii
ACKNOWLEDGMENTS
The work reported was funded by EPRI under RP1403-19 Boiler R&D for Improved
Coal-Fired Power Plants. The authors thank Mr. Wate Bakker for his supervision and
consultation as EPRI Project Manager. The authors also thank the following plant
managers and engineers at the TVA for providing their unit and for aiding in the
installation and exposure:
TVA Gallatin Station, Unit 2
Bill Stanfield
Robert Beasly
Dan Arnott
William I. Edwards
Dave Phillips
Donnie Wallace
Jeff Hollins
Michael Farrell
Tracy Rippy
TVA Chattanooga TN
John Brooks
Peter Chang
Rich Stangarone
Denton Eady
Blaine Roberts
The authors also express their thanks to Frank McAney of FWEC for his help in
designing the computer monitoring system, for his hard work, devotion, and many
trips to the field to keep the monitoring system operating.
The authors wish to acknowledge other people at FWDC whose work made the
completion of this project possibleIstvan Dojcsanszky and Ed Davis for the
metallographic examination, Gabe Lantos, Paul Lang, Rich Boronski, and Michele
Coslit for the chemical analysis, Werner Seitz for computer plotting, Kim Gabriel for
the installation troubleshooting and field trips, and Judy Forbes for the technical
editing.
While acknowledging the other RP1403-19 team member, Ishikawajima-Harima Heavy
Industries Co., Ltd. for the lab testing, probe manufacture, and consultation through
ix
the project, special thanks go to S. Kihara, R. Ishimoto, and I. Kajigaya. Dr. Kiharas
extensive laboratory test for over 216,760 hours of exposure provided the background
for alloy selection.
EXECUTIVE SUMMARY
In the first half of this century, the development of pulverized coal boilers evolved
gradually, setting the groundwork for the explosion of technology that occurred in the
second half. Steam temperatures rose an average of 3.7C (6.6F)/yr from 1903 to about
621C (1150F) in 1955. However, the excursion above 538C (1000F) was short-lived;
by 1960 most steam generators were designed for 565C (1049F), and by 1970 they
were back to 538C (1000F). There were several reasons for this retreat; one being a
materials problem that at that time defied a technical or economic solution. Materials
that exhibited strength to withstand the higher temperatures and pressures present in
superheaters of these supercritical advanced boilers were available; but they proved to
be especially susceptible to corrosion by certain coals, most notably high-sulfur bituminous coals.
The cause of this type of corrosion was discovered in the late fifties and is now generally accepted to be the presence of liquid alkali-iron-trisulfates on the surface of the superheater and reheater tubes beneath an overlying ash deposit. Approaches to solving
this problem have included changing the fuel or providing protective baffling with
sheaths of corrosion-resistant material around selected tubes. Coal-ash corrosion is a
widespread problem for superheater and reheater tubes, especially where high-sulfur,
high-alkali, and possibly high-chlorine coals are used, and is a critical problem which
needs to be resolved before advanced ultra-supercritical boilers can be deployed.
Substantial progress has been made through laboratory testing; however, to verify conclusions drawn from these tests, actual utility service exposures are necessary. In addition, field exposures allow for the evaluation of a number of important environmental
parameters that cannot be fully simulated in the laboratory tests. These parameters
include:
The actual composition of the deposits formed on the tubes is more complex than
the composition of the simulated ash in laboratory tests.
The SO3 concentration formed by heterogeneous reaction on cooled surfaces is variable.
The temperature gradients that occur within the ash deposits are very large.
xi
The ash and flue gas move past tubes at high velocity; the rate varies with design.
The composition of the corrosive deposits changes with time.
The temperatures are not constant.
The effect of fly-ash erosion results in the removal of the protective oxides from the
tube and replenishes the metal surface with fresh corrosive, molten sulfate ash.
As part of RP1403-19, Boiler R&D for Improved Coal-Fired Power Plantssponsored

by the Electric Power Research Institute (EPRI), Foster Wheeler Development Corporation (FWDC), and Ishikawajima-Harima Heavy Industries Co., Inc. (IHI)combined
laboratory and field testing were performed. The results of the laboratory tests for over
216,000 hours with 22 materialsthree alkali-sulfate levels, three levels of SO2, and four
temperaturesreported in EPRI GS-6449, indicate that the alkali and sulfur content,
along with the metal operating temperature, can have a significant effect on coal-ash
corrosion. The loss from corrosion increases with higher levels of SO2, alkali sulfates,
and temperature. The temperature for the maximum corrosion rate, as shown by a bell
curve, shifts and varies in width as a function of alloy composition, SO2, alkali, and
CaO. Pitting attack is not an active mechanism at low levels of SO 2 and alkali, but it
does become activeespecially on chromized coatingsat very high levels of SO 2 and
alkali-sulfate concentrations. Also, chromium was found to be the most beneficial
alloying element for enhanced corrosion resistance. The corrosion resistance was
greatly improved when chromium levels exceeded 25 percent. Laboratory tests have
indicated that standard Type 347 tube material is adequate for mildly corrosive environments, but Type 310 or Type 310 HCbN (Sumitomo HR3C, ASME code case 2115) is
required for more corrosive conditions.
The second phase of RP1403-19 involved field tests exposing eight alloys on air-cooled,
retractable corrosion probes for up to 16,000 hours. FWDC and EPRI chose three boilers,
two burning Eastern high-sulfur and one burning Western low-sulfur, for test probe
exposures. The air-cooled, retractable corrosion probes were designed and installed;
they exposed eight metal samples for 4000, 12,000, and 16,000 hours. In both of the units
burning the high-sulfur Eastern coal, the classic alkali-iron-trisulfate attack occurred. As
expected, chromium was the most beneficial element that improved coal-ash corrosion
resistance in these tests. Alloys with 22 percent or more chromium generally showed
satisfactory corrosion resistance. The boiler burning the low-sulfur Western coal
produced atypical reducing conditions on the backside of the corrosion probes. This
resulted in high corrosion rates, from sulfidation in the presence of calcium sulfate, on
the backside of the tube, rather than at the 2 and 10 oclock positions on the front of the
tube, which is typical for coal-ash corrosion. (EPRI report TR-103438)
The results from the field corrosion probe exposures confirmed the performance of alloys in the laboratory-derived tests (EPRI Report GS-6449). The laboratory corrosion
xii
test data for various coals predicted 1.19 mm (47 mils)/yr for 17-14 CuMo and 0.13 mm
(5 mils)/yr for Type 310. The Gallatin field data measured 0.43 to 1.02 mm (17 to 40
mils)/yr for 17-14 CuMo and 0.05 to 0.15 mm (2 to 6 mils)/yr for Type 310. The combination of the laboratory and field data provided a data base for alloy selection.
Taking into consideration the above factors, HR3C stainless steel was selected as the
preferred material for further long-term testing in a utility boiler. TVAs Gallatin
Station (unit 2), which had experienced excessive coal-ash corrosion in the superheater
and reheater sections of its boilers (resulting in only an average 7-year tube life), was
selected to host this further testing of pressurized specimens or spools. X-ray
diffraction of the corrosion products from tubes removed from the Gallatin unit 2
superheater disclosed the presence of potassium-iron-trisulfate. Platen and pendant
sections [totaling 9450 m (31,000 ft) of tubing] of the reheater in unit 2 were replaced
with tubing made from HR3C material.
In addition to the replacement of the platen and pendant sections with 9450 m of HR3C
tubing, test sections made of other materials showing adequate resistance to coal-ash
corrosion in the probe tests were incorporated in the reheater (Figure ES-1 and Table
ES-1). In the first row (inlet legs) of the platen section (test area 3), seven inlet tubes
contained portions of tubes over which sleeves of different materials were installed.
The sleeves contained three sectionseach approximately 15.24 cm (6 in.) longof the
same material, but with a varying gap between the tube OD and the sleeve ID to obtain
outside sleeve temperatures as close to 621C (1150F), 677C (1250F), and 704C
(1300F) as possible. Because of low inlet steam temperature, the need for variable
gapping was necessary in order to achieve the desired metal temperatures.
Table ES-1
Chemical Composition of Alloys Tested
Alloy
Element
Ni
Cr
Mo
T22
(chromized)
2.25
1.0
304
19
347
19
800H
21
NF709
20
HR3C
25
CR30A
48
30
Ti
Al
Nb
0.8
0.50
0.50
1.5
0.2
0.5
2.0
0.25
0.25
0.25
xiii
Figure ES-1
Location of test areas in reheater
xiv
Two sets of tubular spool sections were assembled in the pendant section of the
reheater. These test sectionswhich contained alloy tubes of Type 304, Type 347,
800H, NF709, and CR30A, in addition to two HR3C sampleswere welded into the
inlet (test area 2) and outlet (test area 1) legs of pendants 10, 25, and 40 (numbered from
the south wall of the boiler). To obtain higher metal temperatures in the reheater loops
containing the in-line test spools (pendant panels 10, 25, and 40), flow-restriction
orifices were installed at the inlet reheater header. By adding these orifices to the
loops, it was hoped to achieve metal temperatures in the vicinity of 635C (1175F) to
649C (1200F) in these pendant test sections. This would be more representative of the
future operating conditions for the advanced power plant. The temperatures actually
achieved, however, were somewhat lower [604-632C (1119-1171F) in test area 1 and
565-618C (1051-1145F) in test area 2]. Gallatin unit 2 commenced operation with the
replacement reheater in April 1991. At this time the boiler employed standard coalfired burners; in November 1994, low-NO x burners were installed.
The test program was successfully completed in 1998 after 45,004 hours of operation
without any forced outages caused by corrosion-induced tube failures in the reheater.
The use of multiple test sections allowed for the collection of data across a wide temperature band [516-685C (960-1260F)] in addition to the monitoring of the operating
behavior in different areas of the reheater, not only from front to back, but across the
bank as well. This report discusses the evaluation of samples from test areas 2 and 3.
Spool sections in the outlet legs of pendants 10, 25, and 40 (test area 1), which showed
very little wastage, are still in service.
Tube wastage was mainly in the form of metal loss, at the 2 and 10 oclock positions,
caused by corrosion/erosion by fly ash-laden flue gas. In addition, the tube surfaces in
the wasted areas were also usually pitted. On the basis of the location and morphology
of the attacked areas, together with the analysis of the ash deposits/scale disclosing the
presence of potassium-iron-trisulfate, the corrosion portion of the wastage was attributed primarily to liquid-phase (coal-ash) corrosion. Accompanying the loss of metal in
the specimens was internal carburization and sulfidation. While sulfur was detected in
all of the surface scales on the specimens and as subsurface sulfides in most of the
alloys, the process that resulted in the deepest internal penetration was carburization.
These carburized zones were probably caused by carbon in the fly ash deposits on the
tubes. It was interesting to note that carburization was also detected in the samples that
were exposed on the ORNL air-cooled, retractable probe that was installed in November 1994, but was not very prominent in the samples exposed on the EPRI probe
(September 1987 to October 1990). Since the low-NOx burners were installed in November 1994, the observation of carburization in the samples from the ORNL probe and
the spool/sleeve sections from this study appears to correlate with the installation of
these burners.
The dependence of the coal-ash corrosion mechanism on temperature is typically characterized by a bell-shaped curve. The wastage increases as the temperature rises in the
xv
range ([600-700C (1112-1292F)] where molten alkali-iron-trisulfates are stable. As the

temperature rises above this range, the wastage decreases because of the dissociation of
the alkali-iron-trisulfates. The temperature at which the maximum wastage occurs is
somewhat different for each alloy, since the temperature range in which the molten salt
is stable depends on the interaction of the corrodent with the metal surface and its resultant corrosion products. For the alloys that exhibited this trend, the temperature at
which the corrosion peaked was 635C (1175F) for Type 304, 621C (1150F) for Type
347 and 800H, 616C (1140F) for NF709, and 632C (1170F) for HR3C.
One of the important results of the test was the observation that the wastage rates of the
various alloys exhibited a dependence on location. Wastage rates were slightly lower
in the platen section (test area 3) than in the pendant section (test area 2) for the same
location, left to right in the boiler, Table ES-2. In the pendant section (test area 2) alone,
however, there was a large variation in corrosion rate across the boiler. The corrosion
rate of most alloys increased from spool 10 to spool 25 and peaked in spool 40. In two
of the three spools (spools 10 and 25), the HR3C sample at the top exhibited higher
wastage rates, by a factor of 2.5 and 1.5 respectively, than the sample at the bottom,
suggesting there may be a difference in the corrosiveness of the environment from top
to bottom as well [covering a span of only 0.9 m (3 ft)].
Table ES-2
Wastage Rates From Spool 25 and Sleeve Sections
Sample
Temperature
C (F)
MMW [py (mpy)]
Spool 25
(Test Area 2)
Sleeve
(Test Area 3)
304H
582 (1079)
610 (24)
457 (18)
347
581 (1078)
330 (13)
533 (21)
800H
582 (1079)
508 (20)
406 (16)
NF709
581 (1078)
330 (13)
330 (13)
HR3C
581 (1077)
356 (14)
254 (10)
CR30A
581 (1078)
152 (6)
102 (4)
Increasing chromium content improved the corrosion resistance of the alloys (Figures
ES-2 and ES-3). This is not an unexpected trend. In all but one case (i.e., spool 10), the
CR30A material, which contains the highest chromium level of the materials tested, exhibited the lowest wastage rates. Unfortunately, at the most corrosive locations (spools
xvi
Figure ES-2
Variation of maximum metal wastage with chromium content for spool specimens
Figure ES-3
Variation of maximum metal wastage with chromium content for sleeve specimens
xvii
40 and 25 in test area 2), none of the alloys displayed acceptable corrosion resistance.
Fortunately, the total area which exhibited unacceptably high corrosion rates was
small, consisting of approximately 20 to 30 tube segments, each about 3 m (10 ft) long.
Most importantly, the alloy of choice, HR3C, performed well in all other areas.
The corrosion rate data obtained from the EPRI and ORNL probes exposed from September 1987 through October 1990 and November 1994 through February 1997 are
compared with the rates obtained in this study for the same alloys in similar areas in
Table ES-3. With the exception of the Type 347 alloy, the wastage rates of alloys from
the EPRI and ORNL probes are about the same, despite the fact that the specimens
were carburized on the latter probe and not the former. This indicates that the use of
low-NOx burners did not have a marked effect on reheater corrosion, at least in this
boiler.
In summary, the results of this program indicate that if the tubes are exposed to operating conditions favorable for coal-ash corrosion, the boiler location, in addition to tube
temperature, is a key variable that affects the wastage rate. The exact parameters governing the aggressiveness of the location are not known but are believed to include the
velocity and temperature of the flue gas, the heat flux, and the ash deposition rate. In
addition, since the samples operated close to the expected tube-metal temperatures for
an advanced ultra-supercritical power plant, some information regarding tube material
selection can be gleaned. In many areas, there are alloys that will perform reasonably
well. However, in a limited number of zones, none of the alloys tested will have adequate lives. Shielding or the use of 40-50 Cr weld overlays may be needed at these
locations. Because the number of highly corroded areas was limited, it is believed that
for most boilers and most fuels, the results of this program provide sufficient data to
select superheater and reheater alloys for ultra-supercritical power plants.
xviii
CONTENTS
1 INTRODUCTION ................................................................................................................. 1-1

2 DATA ACQUISITION SYSTEM AND THERMAL EXPOSURE RESULTS.......................... 2-1
Data Output ........................................................................................................................ 2-2
3 COAL UTILIZATION............................................................................................................ 3-1
4 CHARACTERIZATION AND ULTRASONIC MEASUREMENTS OF TEST
SPECIMENS........................................................................................................................... 4-1
5 METALLURGICAL EVALUATION AND RESULTS ............................................................ 5-1
Visual Examination ............................................................................................................. 5-1
Test Area 2 ..................................................................................................................... 5-1
Test Area 3 ..................................................................................................................... 5-8
Wall Thickness Measurements ......................................................................................... 5-20
Analysis of Ash Deposits/Scale ........................................................................................ 5-23
Metallurgical Evaluation .................................................................................................... 5-25
Wastage Rates ................................................................................................................. 5-41
6 DISCUSSION ...................................................................................................................... 6-1
7 CONCLUSIONS .................................................................................................................. 7-1
8 REFERENCES .................................................................................................................... 8-1
xix
LIST OF FIGURES
Figure ES-1 Location of test areas in reheater ........................................................................ xiv
Figure ES-2 Variation of maximum metal wastage with chromium content for spool
specimens ....................................................................................................................... xvii
Figure ES-3 Variation of maximum metal wastage with chromium content for sleeve
specimens ....................................................................................................................... xvii
Figure 1-1 Comparison of allowable stresses at various temperatures for candidate
alloys............................................................................................................................... 1-6
Figure 1-2 Configuration of reheater in TVA Gallatin Unit 2 (561 Ft-8 in = 171.2 m) .............. 1-7
Figure 1-3 Sleeved Test Assemblies (Test Area 3) [1 in. = 25.4 mm]..................................... 1-9
Figure 1-4 Tubular spool sections (Test Area 1 and 2) [ 1in. = 25.4 mm] ............................. 1-10
Figure 1-5 Location of test areas in reheater ........................................................................ 1-12
Figure 2-1 Variation in average monthly temperature for pendant 10 (spool 10 in test
area 2) and flue gas ........................................................................................................ 2-5
area 2) and flue gas ........................................................................................................ 2-6
area 2) and flue gas ........................................................................................................ 2-7
Figure 2-4 Variation in average monthly temperature for platen 8 (sleeve 8 in test area
3)..................................................................................................................................... 2-8
Figure 2-5 Variation in average monthly temperature for platen 9 (sleeve 9 in test area
3)..................................................................................................................................... 2-9
Figure 2-6 Variation in average monthly temperature for platen 10 (sleeve 11 in test
area 3 ).......................................................................................................................... 2-10
area 3)........................................................................................................................... 2-11
area 3)........................................................................................................................... 2-12
area 3)........................................................................................................................... 2-13
area 3)........................................................................................................................... 2-14
Figure 4-1 Corrosion rate measurements for the 304 stainless steel in test sections 1, 2
and 3 after 26,500 hours................................................................................................. 4-2
xxi
Figure 4-2 Corrosion rate measurements for the HR-3C alloy in test section 1, 2 and 3
after 26,500 hours........................................................................................................... 4-4
Figure 4-3 Corrosion rate measurements for the HR-3C alloy tubing in each element at
elevation 556 feet in test area 2 ...................................................................................... 4-5
Figure 4-4 Corrosion rate measurements for test spools in test area 2 .................................. 4-7
Figure 5-1 Gas-Side Half of Spool 10 (44,712 hours) and Sections Showing Condition
of Surface After Grit Blasting........................................................................................... 5-2
Figure 5-4 Deposits and scale on in-situ spool sections (bottom: HR3C section on spool
10, top: Cr30A section on spool 40)................................................................................ 5-5
Figure 5-5 Heavier multicolor deposit buildups on HR3C tubes above spool 25 .................... 5-6
Figure 5-6 Deposit on horizontal and vertical legs of pendants 19, 20, and 29 ...................... 5-7
Figure 5-7 Cross sections of specimens on spool 10 ............................................................. 5-9
Figure 5-8 Cross sections of specimens on spool 25 ........................................................... 5-10
Figure 5-9 Cross sections of specimens on spool 40 ........................................................... 5-11
Figure 5-10 Difference in surface condition in horizontal and vertical legs of pendants
19 and 20 ...................................................................................................................... 5-12
Figure 5-11 Cross sections of horizontal and vertical legs in pendants 19 and 20. (Bold
arrows indicate direction of flue gas flow) [in. = 25.4 mm]............................................. 5-13
Figure 5-12 Gas-side half of sleeve sections on platens 8 through 11 (45,004 hours) ......... 5-14
Figure 5-13 Gas-side half of sleeve sections on platens 12 through 14 (45,004 hours) ....... 5-15
Figure 5-14 Surface condition of gas-side half of sleeve sections (45,004 hours)................ 5-16
Figure 5-15 Cross sections from section 1 of sleeves on platens 8 through 14.................... 5-17
Figure 5-18 Elemental X-ray spectrums if deposit/scale material on tubes in test area 2..... 5-26
Figure 5-19 Elemental X-ray spectrums of deposit/scale material on sleeve sections in
test area 3 ..................................................................................................................... 5-27
Figure 5-20 Morphology of scale layer and carbon rich patches (bottom right) on
specimen surface .......................................................................................................... 5-28
Figure 5-21 Type 304H: Scale layer on specimen from spool 25 ......................................... 5-31
Figure 5-22 Type 304H: Carburization below scale layer on specimens from spool 25
(top) and spool 40 (bottom)........................................................................................... 5-32
Figure 5-23 Type 304H: X-ray maps for oxygen, sulfur, chromium and nickel in scale on
specimen from spool 25 ................................................................................................ 5-33
Figure 5-24 Type 304H: Scale layer on and subsurface carburization in sleeve section
1 (Platen 9) ................................................................................................................... 5-34
xxii
Figure 5-25 Type 347: Scale layer on and subsurface carburization in specimens from
spool 25 (top and middle) and spool 40 (bottom).......................................................... 5-35
Figure 5-26 Type 347: Scale layer on and subsurface carburization in sleeve section 1
(platen 10)..................................................................................................................... 5-36
Figure 5-27 800H: Scale layer on and subsurface sulfidation in specimen from spool 25 .... 5-37
Figure 5-28 800H: Carburization in specimens from spool 25 (top) and spool 40
(bottom)......................................................................................................................... 5-38
Figure 5-29 800H: X-ray maps for oxygen, sulfur, chromium, and nickel in scale on
specimen from spool 25 ................................................................................................ 5-39
Figure 5-30 800H: Scale layer on and subsurface sulfidation and carburization in sleeve
section 1 (platen 11)...................................................................................................... 5-42
Figure 5-31 800H: Scale layer on sleeve section 2 (platen 11) ............................................ 5-43
Figure 5-32 CR30A: Scale layer on and subsurface sulfidation in specimen from spool
25 .................................................................................................................................. 5-44
Figure 5-33 CR30A: Carburization in specimens from spool 25 (top) and spool 10
(bottom)......................................................................................................................... 5-45
Figure 5-34 CR30A: Scale layer on and subsurface sulfidation and carburization in
sleeve section 1 (platen 14) .......................................................................................... 5-46
Figure 5-35 CR30A: Scale layer on sleeve section 2 (Platen 14) ......................................... 5-47
Figure 5-36 N8709: Scale layer on specimen from spool 25 ................................................ 5-48
Figure 5-37 NF709: Intergranular oxidation and sulfidation in specimen from spool 40 ....... 5-49
Figure 5-38 NF709: Carburization in specimens from spool 25 (top) and spool 40
(bottom)......................................................................................................................... 5-50
Figure 5-39 Scale layer on and subsurface sulfidation and carburization in sleeve
section 1 (platen 12)...................................................................................................... 5-51
Figure 5-40 NF709: Scale layer on sleeve section 2 (platen 12) .......................................... 5-52
Figure 5-41 HR3C: Scale layer on and subsurface sulfidation in HR3C specimen on
spool 25 ........................................................................................................................ 5-53
Figure 5-42 HR3C: Carburization in specimens from spool 25 (top) and spool 40
(bottom)......................................................................................................................... 5-54
Figure 5-43 HR3C: Scale layer in and subsurface sulfidation in sleeve section 1 (Platen
13)................................................................................................................................. 5-55
Figure 5-44 HR3C: Carburization in sleeve section 1 (platen 13) ......................................... 5-56
Figure 5-45 Scale layer on sleeve section 2 (platen 13) ....................................................... 5-57
Figure 5-46 T22Cr: As supplied chromized layer (top-0.013 in. thick) and corroded area
in sleeve section 1 (bottom-platen 8) ............................................................................ 5-58
Figure 5-47 T22Cr: Corroded areas in sleeve section 2 (top) and sleeve section 3
(middle and bottom) ...................................................................................................... 5-59
Figure 5-48 Maximum metal wastage of specimens on spool 10 ......................................... 5-60
xxiii
Figure 5-51 Maximum metal wastage of section 1 specimens on sleeves............................ 5-63

Figure 5-52 Maximum metal wastage of section 2 specimens on sleeves............................ 5-64
Figure 5-53 Maximum metal wastage of section 3 specimens on sleeves........................... 5-65
Figure 5-54 Variation of maximum metal wastage with chromium content for spool
specimens ..................................................................................................................... 5-66
Figure 5-55 Variation of maximum metal wastage with chromium content for sleeve
specimens ..................................................................................................................... 5-67
Figure 5-56 Variation of wastage rates with temperature for spool specimens..................... 5-68
Figure 5-57 Variation of wastage rates with temperature for sleeve specimens ................... 5-69
Figure 5-58 Variation of wastage rates with temperature (combined data for spools and
sleeves, includes results from ORNL and EPRI probes) ............................................... 5-70
xxiv
LIST OF TABLES
Table ES-1 Chemical Composition of Alloys Tested................................................................ xiii
Table ES-2 Wastage Rates From Spool 25 and Sleeve Sections ........................................... xvi
Table 1-1 Chemical Composition of Alloys Tested.................................................................. 1-8
Table 2-1 TVA Gallatin Reheater Instrumentation Channel Assignments .............................. 2-1
Table 2-2 Average Temperatures of Thermocouples in Pendant and Platen Sections .......... 2-3
Table 3-1 Coal-Ash AnalysisGallatin ................................................................................... 3-2
Table 5-1 Wall Loss in Spool Sections ................................................................................. 5-20
Table 5-2 Wall Loss in Sleeve Sections................................................................................ 5-21
Table 5-3 Deposit/Scale Analysis ......................................................................................... 5-24
Table 5-4 Penetration in Spool Sections............................................................................... 5-25
Table 5-5 Penetration in Sleeve Sections............................................................................. 5-29
Table 6-1 Wastage Rates From Spool 25 and Sleeve Sections ............................................. 6-3
Table 6-2 Wastage Rates of Alloys Exposed on EPRI/ORNL Probes and Sleeve/Spool
Sections .......................................................................................................................... 6-6
xxv
2
DATA ACQUISITION SYSTEM AND THERMAL
EXPOSURE RESULTS
Table 2-1 lists the location of 40 thermocouples and their respective channels used to
monitor the temperature of the specimens. The temperatures were recorded every
15 minutes on the Data Acquisition System (DAS). This system reads the milli-volt
output of the individual thermocouples and stores the value in memory. The stored
data are retrieved daily by a central computer at FWDC and processed as required.
Table 2-1
TVA Gallatin Reheater Instrumentation Channel Assignments
Pendant
Thermocouple
Platen
Thermocouple
10
T7 (outlet)
T2
10
T6
T1
10
T5
T0
10
T4
T2
10
T3
T1
10
Flue Gas
T0
25
T7 (outlet)
10
T2
25
T6
10
T1
25
T5
10
T0
25
T4
11
T2
25
T3
11
T1
25
Flue Gas
11
T0
40
T7 (outlet)
12
T2
2-1

Data Acquisition System and Thermal Exposure Results
40
T6
12
T1
40
T5
12
T0
40
T4
13
T2
40
T3
13
T1
40
Flue Gas
13
T0
14
T2
14
T1
14
T0
Cabinet
The DAS system is based on an IBM PC-XT with a 20-MB hard disk and a 2400 BPS
modem. The thermocouples are connected to the computer through a Solartron IMP,
which is an analog to the digital converter and scanner. The IMP is located near the
boiler penetration for the thermocouples in the boiler coal-conveyor tunnel. Although
the IMPs are capable of operating in the ambient conditions [up to 54C (130F)] encountered adjacent to the boiler, they were placed in the conveyor tunnel to allow easier access for maintenance. The IMPs are connected to the computer in the plant control
room with a twisted-wire pair.
The computer operating system does not allow true multitasking in real time. Thus a
time-slicing method allows the computer to communicate over the modem and still
monitor and record the thermocouple data. FWDC personnel can access the computer
through its modem, identify themselves as authorized users through a password, and
download the accumulated data. The computer sets an internal clock every time it interrupts temperature monitoring to transmit data. Throughout the loading process, it
refers to this clock. When a predetermined time has elapsed, it interrupts data transmission and returns to temperature monitoring/recording. It then resets the clock and
continues data transmission where it left off. All data are stored on a 20-MB hard disk
and retained in the event of power failure. When power is restored to the computer, it
automatically restarts itself.11
Data Output
Data output consists of a daily log of all temperatures at 15-minute intervals. Plots of
all data collected can be printed for each detail inlet and outlet thermocouple and the
panel inlet or outlet thermocouple as applicable. These plots can be printed for a daily,
weekly, or monthly period. Plots of flue gas temperature panel inlet and outlet tem2-2

peratures can be generated. A table of monthly averaged temperatures for each channel is also available on demand.
The average temperatures of the thermocouples for the test periods is given in Table 2-2
along with the average temperature of the respective outlet tubes for the pendant sections and inlet tubes for the platen sections. Plots showing the variation in the average
monthly temperatures are displayed in Figures 2-1 through 2-10.
Table 2-2
Average Temperatures of Thermocouples in Pendant and Platen Sections
Pendant
(Test Area 1)
Top Specimen
T6
[C (F)]
Bottom Specimen
T5
[C (F)]
Outlet Tube
T7
[C (F)[
Flue Gas
[C (F)[
10
625 (1158)
621 (1150)
556 (1032)
757 (1395)
25
629 (1164)
633 (1171)
560 (1040)
817 (1503)
40
631 (1168)
604 (1119)
568 (1055)
762 (1405)
Pendant
(Test Area 2)
Top Specimen
T3
[C (F)]
Bottom Specimen
T4
[C (F)]
Outlet Tube
T7
[C (F)]
10
566 (1051)
588 (1091)
556 (1032)
25
582 (1079)
581 (1077)
560 (1040)
40
604 (1119)
618 (1145)
568 (1055)
Platen/Material
(Test Area 3)
Top Sleeve
T1
[C (F)]
Bottom Sleeve
T2
[C (F)]
Inlet Tube
T0
[C (F)]
8/T22Cr
585 (1085)
522 (972)
370 (698)
9/304
663.(1225)
600 (1113)
369 (696)
10/347
639 (1182)
564 (1048)
369 (697)
11/800H
657 (1214)
532(989)
370 (698)
12/NF709
632 (1170)
565 (1049)
369 (696)
13/HR3C
685 (1265)
573 (1063)
370 (698)
14/CR30A
598 (1109)
526 (979)
369 (697)
2-3

Samples from test area 1 were not removed, and therefore the only results which are
presented for that area are ultrasonic wall thickness measurements in section 11. all
other test data and discussions will be limited to test areas 2 and 3.
2-4

Figure 2-1
Variation in average monthly temperature for pendant 10 (spool 10 in test area 2) and flue gas
2-5

Figure 2-2
2-6

Figure 2-3
2-7

Figure 2-4
Variation in average monthly temperature for platen 8 (sleeve 8 in test area 3)
2-8

Figure 2-5
2-9

Figure 2-6
Variation in average monthly temperature for platen 10 (sleeve 11 in test area 3 )
2-10

Figure 2-7
2-11

Figure 2-8
2-12

Figure 2-9
2-13

Figure 2-10
2-14
3
COAL UTILIZATION
In an ideal field coal-ash corrosion test exposure, only one coal would be burned at the
plant. The practice of burning one coal is not common at many utilities since most have
multiple long-term coal contracts; in fact, many are buying coal on the spot market.
TVAs Gallatin Station burns a number of eastern high-sulfur coals, mainly Pyro, Island
Creek, Warrior, Dotiri, Pattiki, and Constain, which are known to be corrosive and
prone to alkali-iron-trisulfate formation. The coal analysis for the various coals burned
as the primary fuel during these exposures is given in Table 3-1. The Borio Index 29 for
these coals typically ranges from 2.0 to 4.1, and the chloride level is 450 to 3000 ppm.
3-1

Coal Utilization
Table 3-1
Coal-Ash AnalysisGallatin
Description
Island
Creek
Warrior
Pyro
Composite
Pyro
Warren
Dotiri
Pattiki
Lodestar
Constain
Coal Basis,%
Fe2O3
1.50
2.70
1.90
2.05
2.19
2.19
1.71
1.71
1.92
1.60
CaO
0.18
0.47
0.32
0.35
0.28
0.47
0.42
0.33
0.26
0.13
MgO
0.06
0.11
0.09
0.09
0.08
0.09
0.06
0.04
0.07
0.07
CaO + MgO
(Eq.)
0.26
0.63
0.45
0.47
0.39
0.60
0.50
0.39
0.357
0.23
Acid Soluble, ppm(w)

Na2O
161
81
263
86
364
248
325
559
410
313
K2O
1085
1310
1398
1060
1283
1617
1164
921
390
325
K2O (as Na2O

Eq.)
705
916
908
689
834
1051
757
598
250
211
MgO
348
829
572
633
671
716
462
398
340
203
CaO
1203
3498
2099
2248
2087
4272
4305
2646
600
432
Chloride
1490
452
2919
2000
3200
1000
2100
1900
2900
2750
3.2
2.3
4.1
2.3
2.0
Indices
Borio Index
3-2
2.0
2.6
2.5
2.2
2.25

Coal Utilization
Proximate, wt%
Fixed Carbon
53
52
53
52
61
51
52
56
52
56
Volatile Matter
39
37
38
38
28
37
39
37
39
35
Ash
11
10
10
12
Ultimate, wt%
Carbon
74
71
74
72
72
71
74
73
77
76
Hydrogen
Oxygen
Nitrogen
Sulfur
Ash
11
10
10
20
12
13,598
12,926
13,593
13,170
13,290
12,518
13,429
13,252
13,809
13,517
HHV, Btu/lb
Sulfur,%
Sulfatic
Pyritic
1.09
1.66
1.35
0.83
1.29
0.93
0.83
0.88
1.21
1.20
Organic
1.99
1.46
1.91
2.38
2.06
2.26
2.55
2.46
1.99
0.53
Total
3.08
3.12
3.26
3.21
3.35
3.19
3.38
3.34
3.20
1.73
3-3
4
CHARACTERIZATION AND ULTRASONIC
MEASUREMENTS OF TEST SPECIMENS
Prior to service, ultrasonic and micrometer wall thickness measurements were made of
each specimen and recorded based on the test specimen identification. The measurements were made at the 0-, 45-, 180-, and 315-degree locations, with the 0-degree location referenced as the expected center of the gas-side half (i.e., the side facing the oncoming flue gas). Two sets of micrometer measurements were madeone approximately 3.2 cm (1-1/4 in.) from the top of the specimen and the other approximately 3.2
cm (1-1/4 in.) from the bottom. In the case of the ultrasonic measurements, one set at
the center of the specimens was obtained.
The ultrasonic thickness calibration block for all specimens was a 6.82-cm (2-11/16 in.)
OD ring, 2.22 cm (0.875 in.) long with a 0.70-cm (0.276-in.) wall made of HR3C material. This ring is stored along with the material archive samples for calibration of the
ultrasonic measurement device on future measurements.
TVA Gallatin unit 2 was shut down for four extended outages after the reheater replacementthe first in October 1993 after 19,815 hours, the second in September 1994
after 26,500 hours, the third in October 1996 after 35,135 hours, and the fourth in March
1998 after 45,004 hours of operation. During the third outage, only test area 2 was accessible for measurements. In the fourth outage, the samples from test areas 2 and 3
were removed, and, therefore, only test area 1 was ultrasonically measured. The inspections revealed variable corrosion rates in different areas of the reheater. These
variations were found both from front to back (platen to pendant) and at different elevations in a given area. Figure 4-1 shows the corrosion rate for the Type 304 stainless
steel for test areas 1, 2, and 3. The first number at each point is the area, the second is
the element.
Conditions in test area 1 were much less corrosive than in test areas 2 and 3, even though
the metal temperature was higher [616 to 635C (1140 to 1175F)] here. This conclusion is
based not only on the significantly lower wastage rate of the Type 304 specimen in this
area compared to the rates in test areas 2 and 3 (Figure 4-1), but also on the absence of
any apparent visual distress in the specimens each time the ultrasonic
4-1

Characterization and Ultrasonic Measurements of Test Specimens
Figure 4-1
Corrosion rate measurements for the 304 stainless steel in test sections 1, 2 and 3 after 26,500 hours
4-2

survey was performed. The lack of substantive corrosion in test area 1 may be due to
several of the following possibilities, either singly or in combination:
Low flue gas temperature in this area
The installation of the test sections on the trailing tubes of the pendants where flue
gas velocity may not be a factor
The correlation of the high specimen temperatures with the downward side of the
bell-shaped curve for corrosion.
Conditions in test area 2 were the most corrosive for the entire reheater. However, actual corrosion rates, both on the test sections and from quality-assurance measurements
of the reheater tubing, varied significantly, both laterally and vertically. Corrosive attack in the area around element 40 was especially severe. Our data from the test section
(Chapter 5) showed a strong correlation with temperature, but analysis of all the ultrasonic data indicates that spatial variations probably also played a major role. Such
variations may be caused by local differences in flue gas temperature, velocity, and flyash content. Corrosion in test area 3 was also relatively high, as may be expected from
the high metal and flue gas temperatures. The corrosion-rate curve indicates that the
bell-shaped curve may indeed exist. The actual reheater tubing, which is at lower
metal temperatures than the test sections, did not suffer the same high wastage.
Figure 4-2 shows the corrosion rates of HR3C in all three areas. Corrosion in test area 1
was again very low, whereas the corrosion in test area 3 again decreases at the highest
temperatures, with a maximum corrosion rate of approximately 0.3 mm/yr (12
mils/yr) at 635C (1175F) This is two to three times lower than that of Type 304, confirming results from previously installed corrosion probes and experience at the Central
Electric Generating Board. Corrosion in test area 2 was generally much higher and
showed a strong temperature or area dependence. The two data points for each element represented the top and bottom of the test section about 0.9 m (3 ft) apart. Corrosion at the bottom of the test piece was consistently lower than that on the top, despite
the fact that the temperature there was 5.5 to 14C (10 to 25F) higher. In the most corrosive areaelement 40the difference in corrosion resistance between HR3C and
Type 304 narrowed considerably to about 25 percent.
In the April 1993 and the September 1994 outages, wall thicknesses of the lead tube in
each element of test area 2 were ultrasonically measured by TVA personnel. In March
1998, only some of the lead tubes were measured by TVA because of the extensive use
of shielding on the lead tubes after 1994. The results of these measurements on the
HR3C tubes are shown in Figure 4-3. This figure illustrates the wide variation in wastage rate from the left to the right side of the boiler at the test area 2 location. The most
aggressive area is from about element 23 to element 42. Also, the wastage rate prior to
4-3

Figure 4-2
Corrosion rate measurements for the HR-3C alloy in test section 1, 2 and 3 after 26,500 hours
4-4

Figure 4-3
Corrosion rate measurements for the HR-3C alloy tubing in each element at elevation 556 feet in test area 2
4-5

April 1993 seemed to be higher than the rate measured in the other two time frames.
Before an absolute conclusion is drawn on this fact, however, it must be realized that
these rates are based on ultrasonic thickness measurements which may have some error
associated with the technique used in obtaining them. A destructive wall thickness
measurement, including subsurface penetration, is always a better measurement of the
extent of corrosion.
FWDC performed ultrasonic wall thickness measurements on the test samples in each
test area when it was accessible. Test area 2 was always accessible; therefore, the results for that area are shown in Figure 4-4. This figure illustrates that, in general, the
order of aggressiveness from lowest to highest was 10, 25, and 40. Also, the wastage
for each material in a given location from 1991 to 1996 was about equal.
4-6

Figure 4-4
Corrosion rate measurements for test spools in test area 2
4-7
5
METALLURGICAL EVALUATION AND RESULTS
Each of the spool sections from test area 2 and sleeve sections from test area 3 was
submitted to a laboratory evaluation that included the following tasks:
Visual examination
Wall thickness measurements (micrometer)
Analysis of ash/deposits
Metallurgical evaluation (microscopic and SEM/EDX)
Determination of wastage rates.
[Note: The spool sections from test area 1 had not been removed from the unit.]
Visual Examination
Test Area 2
The appearance of the in-line test spools from pendants 10, 25, and 40 is illustrated in
Figures 5-1 through 5-3 along with a narrow section depicting the surface condition of
the gas-side half of each sample after grit blasting. [Note: The narrow section was removed from the bottom of the specimen and was one of the sections used for subsequent wall thickness measurements.] In each case, the test spools did not contain any
significant buildup of ash deposits. Rather, the gas-side half exhibited thin, tannishbrown patches atop a metal surface that had a black or greenish-black coloration, as illustrated in the photographs of in situ test specimens in Figure 5-4. The thin deposits
were more apparent on the spool section from pendant 10, whereas the darkened metal
surface condition dominated the appearance of the spools from pendants 25 and 40.
The back half of the spools was essentially smooth and clean, exhibiting only a thin,
brown scale.
In contrast to the test spools, the HR3C tube sections, at the bend just above the location
of the spools, contained a zone of more notable deposit buildup (primarily on the
5-1

Metallurgical Evaluation and Results
Figure 5-1
Gas-Side Half of Spool 10 (44,712 hours) and Sections Showing Condition of Surface After Grit Blasting
5-2

Figure 5-2
5-3

Figure 5-3
5-4

Figure 5-4
Deposits and scale on in-situ spool sections (bottom: HR3C section on spool 10,
top: Cr30A section on spool 40)
5-5

Figure 5-5
Heavier multicolor deposit buildups on HR3C tubes above spool 25
5-6

Figure 5-6
Deposit on horizontal and vertical legs of pendants 19, 20, and 29
horizontal leg) as shown in Figures 5-5 and 5-6. The colors of the deposits were brown,
white, and green. As can be noted in the grit-blasted sections,the surface of the gasside half of each specimen on the three spools exhibited irregularity in the form of
pockmarks and pits. As suggested by the depth of the pockmarks/pits and further
substantiated by the full cross sections shown in Figures 5-7 through 5-9, the amount of
5-7

metal wastage was highest in the specimens from pendant 40 followed, in decreasing
magnitude, by that on the samples from pendants 25 and 10. It is also evident from the
specimens from pendants 40 and 25 that the maximum wastage occurred near the 45and 315-degree (2 and 10 oclock) locations. Furthermore, as can be noted in the specimens pendants 10 and 40, the thickest wall in the on-coming flue gas half was at the top
(0 degrees), whereas in the specimens from pendant 25, the thickness wall was at about
315 degrees. This difference in orientation suggests that the gas flow across pendant 25
may have been slightly skewed toward one side.
Figure 5-10 shows the surface appearance of grit-blasted tube samples removed from
the horizontal and vertical legs of the HR3C sections cut from near the top bend in
pendants 19 and 20. Transverse cross sections with wall thickness measurements are
displayed in Figure 5-11. In both cases, the samples removed from the vertical leg suffered metal wastage while those from the horizontal leg exhibited essentially no wall
loss. The surfaces were pitted and pockmarked similar to those exhibited by the test
samples in the spool sections.
Test Area 3
The appearance of the seven sleeve test sections on platen tubes 8 through 14 is shown
in Figures 5-12 and 5-13. Compared to the test spools from the pendant section, the
outside surface of the sleeves contained more deposit material. The outer layer of the
deposit was tannish brown in color. On some sleeves, primarily the second and third
sections, a white layer and/or white and greenish layer was apparent below the tannish-brown layer. The third sections also appeared to contain more deposit than the
first and second sections. Where the deposits were absent or had spalled off, the metal
surface displayed a black coloration. The back half of the sleeves contained a thin, light
tan deposit.
The surface appearance of the gas-side half is illustrated in Figure 5-14 on grit-blasted
transverse cross sections cut from the bottom of each specimen. Similar to the spool
samples, the specimens exhibited irregular, pockmarked and pitted surfaces, and, as indicated in the full transverse sections displayed in Figures 5-15 through 5-17, the
maximum wastage occurred near the 45- and 315-degree (2 and 10 oclock) locations.
5-8

Figure 5-7
Cross sections of specimens on spool 10
5-9

Figure 5-8
5-10

Figure 5-9
5-11

Figure 5-10
Difference in surface condition in horizontal and vertical legs of pendants 19 and
20
5-12

Figure 5-11
Cross sections of horizontal and vertical legs in pendants 19 and 20. (Bold arrows
indicate direction of flue gas flow) [in. = 25.4 mm]
5-13

Figure 5-12
Gas-side half of sleeve sections on platens 8 through 11 (45,004 hours)
5-14

Figure 5-13
Gas-side half of sleeve sections on platens 12 through 14 (45,004 hours)
5-15

Figure 5-14
Surface condition of gas-side half of sleeve sections (45,004 hours)
5-16

Figure 5-15
Cross sections from section 1 of sleeves on platens 8 through 14
5-17

Figure 5-16
5-18

Figure 5-17
5-19

Wall Thickness Measurements

Except for the spool section from pendant 25, wall thickness measurements (micrometer) were made at the 0-, 45-, 180-, and 315-degree locations in grit-blasted sections
removed from the top and bottom of each test sample. In the spool section from
pendant 25, the thickness measurements were made in a section cut from the samples.
The calculated wall loss at each orientation is given Tables 5-1 (spool sections) and 5-2
(sleeve sections). The maximum wall loss of the HR3C sections removed from the
vertical leg at the top bend in tubes 19 and 20 was 1 (0.042) and 1.3 mm (0.051 in.),
respectively.
Table 5-1
Wall Loss in Spool Sections
Element
Material
Position
Average
Temperature
[C (F)]
5-20
Thickness Loss [mm (in.)]
45
180
315
10
HR3C
566 (1051)
0.56 (0.022) 0.79 (0.031) 0.13 (0.005) 0.86 (0.034)
10
304
T
B
570 (1058)
0.33 (0.013) 0.91 (0.036) 0.10 (0.004) 1.22 (0.048)

0.18 (0.007) 1.07 (0.042) 0.13 (0.005) 1.04 (0.041)
10
800H
T
B
573 (1064)
0.36 (0.014) 0.76 (0.030) 0.10 (0.004) 0.74 (0.029)

0.41 (0.016) 0.79 (0.031) 0.15 (0.006) 0.58 (0.023)
10
347
T
B
577 (1071)
0.33 (0.013) 0.84 (0.033) 0.13 (0.005) 0.91 (0.036)

0.36 (0.014) 0.58 (0.023) 0.10 (0.004) 0.30 (0.012)
10
CR30A
T
B
581 (1077)
0.25 (0.010) 0.28 (0.011) 0.15 (0.006) 0.13 (0.005)

0.13 (0.005) 0.33 (0.013) 0.10 (0.004) 0.36 (0.014)
10
NF709
T
B
584 (1084)
0.20 (0.008) 0.33 (0.013) 0.08 (0.003) 0.23 (0.009)

0.15 (0.006) 0.46 (0.018) 0.10 (0.004) 0.46 (0.018)
10
HR3C
T
B
588 (1091)
0.23 (0.009) 0.18 (0.007) 0.08 (0.003) 0.30 (0.012)

0.20 (0.008) 0.20 (0.008) 0.08 (0.003) 0.18 (0.007)
25
HR3C
582 (1079)
1.17 (0.046) 1.52 (0.060)
25
304
582 (1079)
1.32 (0.052) 1.98 (0.078) 0.03 (0.001
2.11 (0.083)
25
800H
582 (1079)
1.93 (0.076) 1.12 (0.044) 0.15 (0.006
1.68 (0.066)
25
347
582 (1079)
1.12 (0.044) 1.02 (0.040)
0.99 (0.039)
25
CR30A
581 (1078)
0.56 (0.022) 0.38 (0.015) 0.03 (0.001) 0.41 (0.016)
0.000
0.000
1.88 (0.074)

25
NF709
581 (1078)
0.36 (0.014) 1.04 (0.041) 0.03 (0.001) 0.84 (0.033)
25
HR3C
581 (1078)
0.94 (0.037) 1.12 (0.044) 0.03 (0.001) 0.86 (0.034)
40
HR3C
604 (1119)
0.81 (0.032) 1.98 (0.078) 0.03 (0.001) 2.82 (0.111)
40
304
T
B
607 (1124)
0.61 (0.024) 3.46 (0.134) 0.10 (0.004) 3.53 (0.139)

0.51 (0.020) 4.32 (0.170) 0.05 (0.002) 3.86 (0.152)
40
800H
T
B
609 (1128)
0.66 (0.026) 3.38 (0.133) 0.08 (0.003) 3.94 (0.155)

0.30 (0.012) 3.38 (0.133) 0.05 (0.002) 2.92 (0.115)
40
347
T
B
612 (1133)
0.05 (0.002) 2.59 (0.102) 0.05 (0.002) 3.63 (0.143)

0.36 (0.014) 3.73 (0.147) 0.08 (0.003) 3.20 (0.146)
40
CR30A
T
B
614 (1138)
0.000
1.91 (0.075) 0.13 (0.005) 1.93 (0.076)
0.10 (0.004) 1.75 (0.069) 0.05 (0.002) 2.08 (0.082)
40
NF709
T
B
616 (1141)
0.000
3.18 (0.125) 0.03 (0.001) 3.48 (0.137)
0.38 (0.015) 3.35 (0.132) 0.08 (0.003) 3.53 (0.139)
40
HR3C
T
B
627 (1160)
0.41 (0.016) 3.33 (0.131) 0.05 (0.002) 3.28 (0.129)

0.10 (0.004) 3.48 (0.137) 0.08 (0.003) 3.30 (0.130)
Table 5-2
Wall Loss in Sleeve Sections
Element Material Section Position
T22Cr
Average
Temperature
[C (F)]
45
180
315
585 (1085)
0.99
(0.039)
1.32
(0.052)
0.97
(0.038)
0.97
(0.038)
0.20
(0.008)
0.23
(0.009)
0.94
(0.037)
1.09
0.043)
554 (1029)
0.66
(0.026)
0.18
(0.007)
0.18
(0.007)
0.46
(0.018)
0.23
(0.009)
0.30
(0.012)
0.89
(0.035)
0.66
(0.026)
522 (972)
0.13
(0.005)
0.28
(0.011)
0.05
(0.002)
0.10
(0.004)
0.05
(0.002)
0.08
(0.003)
0.08
(0.003)
0.10
(0.004)
663 (1225)
0.61
(0.024)
0.76
(0.030)
1.42
(0.056)
1.35
(0.053)
0.15
(0.006)
0.10
(0.004)
2.31
(0.091)
3.51
(0.138)
T22Cr
T
B
T22Cr
T
B
304
T
B
Thickness Loss [mm (in.)]
5-21

304
637 (1179)
0.94
(0.037)
1.68
(0.066)
1.70
(0.067)
1.83
(0.072)
0.13
(0.005)
0.20
(0.008)
2.03
(0.080)
2.06
(0.081)
601 (1113)
0.84
(0.033)
0.81
(0.032)
2.18
(0.086)
2.03
(0.080)
0.03
(0.001)
0.03
(0.001)
1.30
(0.051)
1.68
(0.066)
639 (1182)
0.33
(0.013)
0.41
(0.016)
1.37
(0.054)
1.83
(0.072)
0.13
(0.005)
0.000
1.91
(0.075)
2.79
(0.110)
602 (1115)
0.51
(0.020)
0.46
(0.018)
1.98
(0.078)
2.24
(0.088)
0.13
(0.005)
0.03
(0.001)
2.69
(0.106)
2.87
(0.113)
564 (1048)
0.58
(0.023)
0.84
(0.033)
1.55
(0.061)
1.42
(0.056)
0.10
(0.004)
0.08
(0.003)
1.47
(0.058)
1.37
(0.054)
657 (1214)
0.66
(0.026)
0.99
(0.039)
1.04
(0.041)
1.07
(0.042)
0.18
(0.007)
0.13
(0.005)
1.93
(0.076)
1.91
(0.075)
594 (1102)
0.71
(0.028)
0.71
(0.028)
1.37
(0.054)
1.75
(0.069)
0.08
(0.003)
0.13
(0.005)
1.93
(0.076)
2.18
(0.086)
532 (989)
0.79
(0.031)
0.69
(0.027)
1.12
(0.044)
1.02
(0.040)
0.000
1.02
(0.040)
1.07
(0.042)
632 (1170)
0.66
(0.026)
0.28
(0.011)
1.24
(0.049)
0.74
(0.029)
0.18
(0.007)
0.08
(0.003)
1.73
(0.068)
1.63
(0.064)
599 (1110)
0.97
(0.038)
0.81
(0.032)
1.65
(0.065)
1.75
(0.069)
0.05
(0.002)
0.10
(0.004)
0.99
(0.039)
1.93
(0.076)
565 (1049)
0.71
(0.028)
0.58
0.86
(0.034)
1.45
0.000
0.74
(0.029)
0.91
304
T
B
10
347
T
B
10
347
T
B
10
347
T
B
11
800H
T
B
11
800H
T
B
11
800H
T
B
12
NF709
T
B
12
NF709
T
B
12
5-22
NF709
0.000
0.03

B
13
HR3C
(0.023)
(0.057)
(0.001)
(0.036)
685 (1265)
0.30
(0.012)
0.18
(0.007)
1.22
(0.048)
0.81
(0.032)
0.03
(0.001)
0.08
(0.003)
1.57
(0.062)
0.58
(0.023)
629 (1164)
0.38
(0.015)
0.56
(0.022)
1.14
(0.045)
1.32
(0.052)
0.03
(0.001)
0.05
(0.002)
1.35
(0.053)
1.19
(0.047)
573 (1063)
0.89
(0.035)
0.43
(0.017)
1.24
(0.049)
1.07
(0.042)
0.000
0.05
(0.002)
0.99
(0.039)
0.86
(0.034)
598 (1109)
0.74
(0.029)
0.38
(0.015)
0.56
(0.022)
0.36
(0.014)
0.23
(0.009)
0.13
(0.005)
0.61
(0.024)
0.28
(0.011)
562 (1044)
0.28
(0.011)
0.25
(0.010)
0.23
(0.009)
0.36
(0.014)
0.18
(0.007)
0.10
(0.004)
0.25
(0.010)
0.18
(0.007)
526 (979)
0.15
(0.006)
0.38
(0.015)
0.10
(0.004)
0.05
(0.002)
0.03
(0.001)
0.03
(0.001)
0.05
(0.002)
0.25
(0.010)
13
HR3C
T
B
13
HR3C
T
B
14
CR30A
T
B
14
CR30A
T
B
14
CR30A
T
B
Analysis of Ash Deposits/Scale

Samples of ash deposit/scale were removed from various locations on the submitted
sections and evaluated by x-ray fluorescence, x-ray microdiffraction, and energy dispersive x-ray (EDX) analysis. The latter analysis was performed in a scanning electron
microscope (SEM).
Since the test spools did not contain any substantial buildup of ash deposits, samples
for analysis were removed from the tubes cut from the top bend in pendants 20, 25, and
29 (Figures 5-5 and 5-6). The results of the analysis on these samples, as well as on
samples removed from the tubes above and below the sleeve test sections are given in
Table 5-3. The results indicate that the deposit/scale samples were comprised mainly
of silicon and aluminum from the ash and iron, chromium, and nickel (as oxides or corrosion product) from the scale. Carbon, a moderate amount of potassium and some arsenic were also detected in both. Comparing the composition of ash at both the locations, the bulk analysis indicates higher concentrations of Ca, Na, S, and C in test area 3
and higher concentrations of Cr, Ni, and As in test area 2.
5-23

To obtain information regarding the elemental makeup of the distinct layers that comprised the deposit/scale, EDX analyses were performed on various tube (test area 2) or
sleeve (test area 3) sections with the deposit/scale intact. The resultant elemental x-ray
spectrums are presented in Figures 5-18 and 5-19. As can be noted, the elemental constituents in the same specific layers at each test area were essentially similar. The results revealed:
The tannish brown or outermost layer of the deposit/scale consisted mainly of coal
ash constituents, namely silicon, aluminum, oxygen, sulfur, iron, potassium, sodium, calcium, and titanium (spectrum A). A small amount of carbon was also detected.
The underlying green layer was predominantly comprised of sulfur, potassium,

oxygen, and iron, with a small amount of sodium (spectrum B). X-ray microdiffraction indicated the presence of iron sulfate [Fe2(SO4)3], potassium-iron-trisulfate
[K3Fe(SO4)3], and sodium sulfate [Na2S2O3].
The white layer contained silicon and oxygen (spectrum C) which were analyzed by
x-ray microdiffraction to be silicon oxide (SiO 2).
The black layer on the metal surface was a chromium-rich scale that contained sulfur, oxygen, and a small amount of carbon (spectrum D). Iron and nickel from the
base material were also detected.
The small patches of a smooth-appearing substance that was sporadically observed

on the scale layer of most specimens evaluated in the SEM was carbon rich
(spectrum E).
Figure 5-20 shows various morphologies of the black scale layer and one of the carbonrich patches (bottom right photomicrograph) on the surface.
Table 5-3
Deposit/Scale Analysis
Compound
5-24
Tubes 20, 25, 29

Test Area 2
Tubes
Test Area 3
SiO2
31.0
31.2
Al2O3
12.8
16.5
TiO2
0.8
1.3
Fe2O3
18.9
24.0
CaO
0.7
4.3

MgO
1.3
1.4
Na2O
0.9
2.2
K2O
9.7
7.3
SO3
3.3
6.8
P2O5
0.5
0.8
As2O5
6.8
1.4
CrO
9.6
2.6
NiO
3.5
1.6
Total C
0.17
0.32
Loss on Ignition
28.9
24.83
Metallurgical Evaluation
Full wall samples were removed from wastage areas of each spool and sleeve sample
for microscopic examination to characterize the wastage morphology. Energy dispersive x-ray (EDX) analysis was used to identify the elemental makeup of surface scales
and the internal penetration species. The depth of penetration was measured and reported in Tables 5-4 and 5-5. Descriptions of the wastage morphology follow.
Table 5-4
Penetration in Spool Sections
Element
Material
Penetration
[mm (in.)]
Element
Material
Penetration
[mm (in.)]
Element
Material
Penetration
[mm (in.)]
10
HR3C
0.15 (0.006)
25
HR3C
0.30 (0.012)
40
HR3C
0.28 (0.011)
10
304H
0.36 (0.014)
25
304H
0.36 (0.014)
40
304H
0.36 (0.014)
10
800H
0.13 (0.005)
25
800H
0.18 (0.007)
40
800H
0.13 (0.005)
10
347
0.25 (0.010)
25
347
0.23 (0.009)
40
347
0.43 (0.017)
10
CR30A
0.10 (0.004)
25
CR30A
0.08 (0.003)
40
CR30A
0.10 (0.004)
10
NF709
0.13 (0.005)
25
NF709
0.25 (0.010)
40
NF709
0.36 (0.014)
10
HR3C
0.05 (0.002)
25
HR3C
0.30 (0.012)
40
HR3C
0.28 (0.011)
5-25

Figure 5-18
Elemental X-ray spectrums if deposit/scale material on tubes in test area 2
5-26

Figure 5-19
Elemental X-ray spectrums of deposit/scale material on sleeve sections in test area 3
5-27

Figure 5-20
Morphology of scale layer and carbon rich patches (bottom right) on specimen
surface
5-28

Table 5-5
Penetration in Sleeve Sections
Element
Section
Material
Penetration
[mm (in.)]
Element
Section
Material
Penetration
[mm (in.)]
T22Cr
12
NF709
0.36 (0.014)
T22Cr
12
NF709
0.23 (0.009)
T22Cr
12
NF709
0.18 (0.007)
304H
0.61 (0.024)
13
HR3C
0.30 (0.012)
304H
0.46 (0.018)
13
HR3C
0.15 (0.006)
304H
0.28 (0.011)
13
HR3C
0.13 (0.005)
10
347
0.48 (0.019)
14
CR30A
0.08 (0.003)
10
347
0.43 (0.017)
14
CR30A
0.03 (0.001)
10
347
0.28 (0.011)
14
CR30A
0.03 (0.001)
11
800H
0.23 (0.009)
11
800H
0.13 (0.005)
11
800H
0.10 (0.004)
*Chromized layer completely consumed in section 1.

Chromized layer breached in some locations in sections 2 and 3.
Type 304The Type 304 samples on the spool sections exhibited a scale layer as
illustrated in Figures 5-21 and 5-22. EDX analysis, Figure 5-23, revealed the scale
was chromium rich and contained iron, sulfur, and oxygen as well. The light gray
constituents in the scale tended to exhibit a higher sulfur level than the bulk scale.
A few sulfide islands were noted in the base metal below the scale. However, after
etching, carburization was noted to a more significant depth as indicated in Figure
5-22.
The sleeve samples contained more of a two-layered scale as displayed in Figure 524. Similar to spool samples, the scale layer adjacent to the metal was mostly chromium, along with iron, sulfur, and oxygen. The outer layer was predominantly
iron oxide with entrapped ash particulate (i.e., spherically shaped particulate).
Etching also indicated each of the three samples was carburized.
Type 347The Type 347 samples on the spool sections also displayed a scale layer
comprised of dark gray (bulk scale) and light gray constituents as illustrated in Figure 5-25. Similar to the Type 340 samples, the bulk scale contained mainly chromium in addition to iron, sulfur, and oxygen; the light gray constituents in the scale
5-29

were sulfur rich; the base metal below the scale contained a few sulfides; and carburization was evident to a more significant depth than sulfidation.
As shown in Figure 5-26, the scale on the sleeve samples exhibited a similar morphology to that on the spool sections. EDX analyses indicated a similar elemental
makeup as well, and etching revealed notable carburization in each sample. An
outer scale layer comprised of iron oxide with entrapped ash particulate was also
evident in some areas.
800HAs displayed in Figures 5-27 and 5-28, the 800H samples on the spool
sections exhibited a gray scale layer which at some locations exhibited white veins
within it. The scale was predominantly chromium oxide with some sulfur, while
the white veins analyzed as nickel sulfide, Figure 5-29. More base metal sulfidation
was apparent in these samples than in the type 304H and 347 samples. The sulfides
were chromium rich and developed in a chromium-depleted zone below the scale.
Carburization was also apparent in each sample after etching.
In the sleeve samples, section 1 (i.e., largest gap between sleeve and tube), Figure 530, showed more internal sulfidation, carburization, and grain boundary oxidation
than the other two sections, which contained a scale layer with some minor internal
sulfidation (Figure 5-31). The scale was mainly chromium oxide with sulfur and
did not exhibit the white veins that were noted in the scale on the spool sections.
CR30AThe scale on the CR30A spool samples, Figure 5-32 and 5-33, contained
chromium, oxygen, and sulfur. Shallow base metal sulfidation, which was in the
form of chromium-rich sulfides, was apparent. Etching (with oxalic acid) revealed a
white band which had a microhardness of up to 55 HRC, compared to base metal
hardness of 35 to 37 HRC. Etching with another solution (FeCl3 plus HCl) indicated
the band was carburized, which would account for the high hardness.
Each of the sleeve sections contained scale and scale with trapped ash constituents
on the surface. Section 1 (Figure 5-34) exhibited more internal sulfidation and carburization than Sections 2 and 3 (Figure 5-35).
NF709As was the case in the 800H samples and illustrated in Figure 5-36 the scale
on the NF709 spool samples contained veins that were high in nickel and sulfur.
Otherwise, the scale was mainly chromium, oxygen, and sulfur. The spool samples
on pendants 40 and 10 exhibited more base metal sulfidation than the sample on
pendant 25. The sample on pendant 40 also displayed some intergranular oxidation
and sulfidation, Figure 5-37. Carburization was also apparent after etching, Figure
5-38, with the deepest penetration occurring in the sample on pendant 40.
5-30

Figure 5-21
Type 304H: Scale layer on specimen from spool 25
5-31

Figure 5-22
Type 304H: Carburization below scale layer on specimens from spool 25 (top) and
spool 40 (bottom)
5-32

Figure 5-23
Type 304H: X-ray maps for oxygen, sulfur, chromium and nickel in scale on
specimen from spool 25
5-33

Figure 5-24
Type 304H: Scale layer on and subsurface carburization in sleeve section 1 (Platen
9)
5-34

Figure 5-25
Type 347: Scale layer on and subsurface carburization in specimens from spool
25 (top and middle) and spool 40 (bottom)
5-35

Figure 5-26
Type 347: Scale layer on and subsurface carburization in sleeve section 1 (platen
10)
5-36

Figure 5-27
800H: Scale layer on and subsurface sulfidation in specimen from spool 25
5-37

Figure 5-28
800H: Carburization in specimens from spool 25 (top) and spool 40 (bottom)
5-38

Figure 5-29
800H: X-ray maps for oxygen, sulfur, chromium, and nickel in scale on specimen
from spool 25
5-39

The scale on the sleeve samples, Figures 5-39 and 5-40, was also mainly chromium
with oxygen, sulfur, and iron. In some areas, an outer scale layer comprised of iron
oxide with entrapped ash particulate was also apparent. White veins rich in sulfur
and nickel were noted in the scale on sections 1 and 2. Section 1 also had intergranular sulfidation/oxidation and more internal sulfidation than sections 2 and 3.
All three sections displayed carburization, with the deepest penetration noted in
section 1.
HR3CThe HR3C spool samples, Figures 5-41 and 5-42, contained scale that was
predominantly chromium, with some iron, oxygen, and sulfur. Light-colored veins,
high in sulfur and nickel, were apparent in the scale on the bottom sample on pendant 25. In several other samples, a light gray constituent that was higher in sulfur
than that in the bulk scale was also noted. with the exception of the top sample on
pendant 25, all of the samples exhibited some base metal sulfidation. Carburization
was evident in each sample, with the depth being equal in the samples on pendants
40 and 25.
The HR3C sleeve samples, shown in Figures 5-43 and 5-44, contained scale that was
also predominantly chromium, with some iron, oxygen, and sulfur. Light gray
constituents in the scale, Figure 5-45, exhibited a higher sulfur content than the bulk
scale. Section 1 displayed internal sulfidation and intergranular
sulfidation/oxidation, while sections 2 and 3 were mostly scale with shallow
sulfidation. Each section was also carburized with section 1 exhibiting
approximately twice the depth as sections 2 and 3.
T22 Chromized (sleeve section only)The appearance of the chromized layer in the
as-supplied condition is shown in Figure 5-46 (top). The layer was approximately
0.33 mm (0.013 in.) thick and was attended by a decarburized zone in the base metal
that was approximately 0.64 mm (0.025 in.) deep. Attack of the chromized layer
was noted to varying degrees in each of the three sections. In section 1, Figure 5-46
(bottom), the chromized layer was missing altogether, and a thick scale comprised
mainly of iron oxide, with scattering of iron sulfide (light gray areas) throughout,
was present. In section 2, Figure 5-47 (top), the chromized layer was missing in
some places and corroded in others; in the corroded areas, carburization was apparent. Although exhibiting evidence of attack, the chromized layer was present in
most areas on section 3. In some localized areas, as shown in Figure 5-47 (middle),
the layer was breached and attack of the underlying T22 base metal had occurred.
Analysis of the scale material in the corroded zones, Figure 5-47 (bottom) revealed
both chromium and iron layers high in sulfur and oxygen. Carburization of the
chromized layer was also noted after etching.
5-40

Wastage Rates
The maximum wastage rate for each sample is shown in Figures 5-48 through 5-53.
Wastage is considered to be both the material consumed (Tables 5-1 and 5-2) and the
metal rendered ineffective as a result of the internal penetration of corrosive species
(e.g., oxides/sulfides) and carburization (from Tables 5-4 and 5-5). The amount of each
type of wastage is indicated in the bar graphs. The variation of wastage rate with
chromium level for the specimens is illustrated in Figures 5-54 and 5-55. The variation
in wastage rates with temperature, for the specimens in each test area, is displayed in
Figures 5-56 and 5-57. A graph of the combined data is shown in Figure 5-58.
5-41

Figure 5-30
800H: Scale layer on and subsurface sulfidation and carburization in sleeve section 1
(platen 11)
5-42

Figure 5-31
800H: Scale layer on sleeve section 2 (platen 11)
5-43

Figure 5-32
CR30A: Scale layer on and subsurface sulfidation in specimen from spool 25
5-44

Figure 5-33
CR30A: Carburization in specimens from spool 25 (top) and spool 10 (bottom)
5-45

Figure 5-34
CR30A: Scale layer on and subsurface sulfidation and carburization in sleeve
section 1 (platen 14)
5-46

Figure 5-35
CR30A: Scale layer on sleeve section 2 (Platen 14)
5-47

Figure 5-36
N8709: Scale layer on specimen from spool 25
5-48

Figure 5-37
NF709: Intergranular oxidation and sulfidation in specimen from spool 40
5-49

Figure 5-38
NF709: Carburization in specimens from spool 25 (top) and spool 40 (bottom)
5-50

Figure 5-39
Scale layer on and subsurface sulfidation and carburization in sleeve section 1
(platen 12)
5-51

Figure 5-40
NF709: Scale layer on sleeve section 2 (platen 12)
5-52

Figure 5-41
HR3C: Scale layer on and subsurface sulfidation in HR3C specimen on spool 25
5-53

Figure 5-42
HR3C: Carburization in specimens from spool 25 (top) and spool 40 (bottom)
5-54

Figure 5-43
HR3C: Scale layer in and subsurface sulfidation in sleeve section 1 (Platen 13)
5-55

Figure 5-44
HR3C: Carburization in sleeve section 1 (platen 13)
5-56

Figure 5-45
Scale layer on sleeve section 2 (platen 13)
5-57

Figure 5-46
T22Cr: As supplied chromized layer (top-0.013 in. thick) and corroded area in
sleeve section 1 (bottom-platen 8)
5-58

Figure 5-47
T22Cr: Corroded areas in sleeve section 2 (top) and sleeve section 3 (middle and
bottom)
5-59

Figure 5-48
Maximum metal wastage of specimens on spool 10
5-60

Figure 5-49
5-61

Figure 5-50
5-62

Figure 5-51
Maximum metal wastage of section 1 specimens on sleeves
5-63

Figure 5-52
5-64

Figure 5-53
5-65

Figure 5-54
Variation of maximum metal wastage with chromium content for spool specimens
5-66

Figure 5-55
Variation of maximum metal wastage with chromium content for sleeve specimens
5-67

Figure 5-56
Variation of wastage rates with temperature for spool specimens
5-68

Figure 5-57
Variation of wastage rates with temperature for sleeve specimens
5-69

Figure 5-58
Variation of wastage rates with temperature (combined data for spools and sleeves, includes results from ORNL and
EPRI probes)
5-70
6
DISCUSSION
This report describes the successful completion of a long-term test program in which
various alloys considered for use in ultra-supercritical coal-fired power plants were exposed to a boiler environment. The use of multiple test sections allowed for the collection of data across a wide temperature band in addition to the monitoring of the operating behavior in different areas of the reheater, not only from front to back, but across
the bank as well. Sample exposure times were for 35,135 and 45,004 hours, while metal
temperatures were in the 521 to 682C (970 to 1260F) range. This report discusses the
evaluation of samples from test areas 2 and 3; spool sections in the outlet legs of pendants 10, 25, and 40 (test area 1) are still in service. Only ultrasonic thickness measurements, which showed the absence of any significant corrosion, were obtained in the
latter area.
As stated previously, wastage is considered to be both the material consumed and the
metal rendered ineffective as a result of carburization and the internal penetration of
corrosive species. As indicated in Figures 5-48 through 5-53, the wastage of the specimens was primarily in the form of consumed metal. In all cases, the surface in the
wasted areas exhibited irregularity in the form of pockmarks and pits, and the maximum wastage occurred at or near the 45- and 315-degree (2 and 10 oclock) locations.
On the basis of these two features and the analysis of the ash deposits/scale which
showed the presence of potassium-iron-trisulfate, the wastage is attributed, in part, to
liquid-phase (coal-ash) corrosion.
Accompanying the loss of metal in the specimens was internal carburization and sulfidation, which were additional mechanisms that contributed to the metal wastage.
While sulfur was detected in all of the surface scales on the specimens and as subsurface
sulfides in most of the alloys, the process that resulted in the deepest internal penetration of an environmental species was carburization. The presence of carburized
zones was not surprising based on the detection of carbon in the deposit/scale removed
from the samples from both test areas and on the microscopic observation of patches of
carbon-rich material in the scale layers. Furthermore, the presence of carburized zones
in all of the specimens indicates the existence of substoichiometric conditions under the
deposits. No conclusion could be drawn, however, as to whether or not the bulk flue
gas was reducing. It was interesting to note that carburization was also detected in the
samples that were exposed on the ORNL air-cooled, retractable probe that was installed
in November 1994 but not very prominent in the samples exposed on the EPRI probe
6-1

Discussion
(September 1987 to October 1990). Since the low-NOx burners were installed in November 1994, it appears likely that the carburization was promoted by these burners,
probably because of an increase of carbon in the flyash.
The dependence of the coal-ash corrosion mechanism on temperature is typically characterized by a bell-shaped curve. The wastage increases as the temperature rises in the
range [600 to 700 C (1112 to 1292F)] where molten alkali-iron-trisulfates are stable. As
the temperature rises above this range, the wastage decreases because of the dissociation of the alkali-iron-trisulfates. The temperature at which the maximum wastage
occurs is somewhat different for each alloy, since the temperature range in which the
molten salt is stable depends on the interaction of the corrodent with the metal surface
and its resultant corrosion products. As can be noted in Figures 5-56 through 5-58, a
bell-shaped curve was apparent for some of the alloys. For the alloys that exhibited this
trend, the temperature at which the corrosion peaked was 635C (1175F) for Type 304,
621C (1150F) for Type 347 and 800H, 616C (1140F) for NF709, and 632C (1170F) for
HR3C.
The samples from spool 40 in test area 2 exhibited the highest wastage rates, followed in
decreasing order by the samples on spools 25 and 10. The tubes in this area have
historically suffered the highest metal loss. The higher wastage rates of the samples on
spool 40 may be explained, in part, by the fact that they were at a higher temperature
than their counterparts on spools 25 and 10. A difference in the boiler environment
(e.g., composition and velocity of flue gas and the amount and composition of the flyash) may have also been a factor since the wastage rates were greater for the specimens
on spool 25 than those on spool 10, yet the metal temperature differences of the specimens on these two spools were not that large. Despite the higher metal temperatures of
the specimens on spool 40, the increase in wastage rates from spool 10 to spool 25 to
spool 40 suggests that the conditions from left to right across the reheater were different. For example, erosion from flyash-laden flue gas appears to have been a factor that
affected spools 40 and 25 more than spool 10, indicating that corrosion/erosion was the
primary wastage mechanism in these specimens. In this case, the erosion may have
acted to remove the protective oxide from the specimens and replenish the surface with
aggressive sulfate ash. Since there were no significant deposit buildups on the specimens, it could not be determined whether the deposit makeup was also a reason for the
variation in the wastage rates.
To assess whether there was a difference in corrosiveness of the environment from front
to back, or between the platen and pendant areas, a comparison was made between the
wastage rates of the specimens on spool 25 with those from the sleeve sections. [Note:
Spool 25 was chosen because it was in line with the sleeve sections with regard to the
on-coming flow of flue gas, and, as a result, the effect of erosion should be
approximately the same in both areas.] The results in Table 5-3 indicated there were
some differences in the makeup of the deposit/scale from both areas. To make the
comparison valid, the wastage rates at the same temperature were compared. For the
6-2

Discussion
sleeve sections, the wastage rates were obtained from Figure 5-57. The corresponding
values from both areas are given in Table 6-1.
Table 6-1
Wastage Rates From Spool 25 and Sleeve Sections
Sample
Temperature
[C (F)]
MMW [py (mpy)]
Spool 25
(Test Area 2)
Sleeve
(Test Area 3)
304
582 (1079)
610 (24)
457 (18)
347
581 (1078)
330 (13)
533 (21)
800H
582 (1079)
508 (20)
406 (16)
NF709
581 (1078)
330 (13)
330 (13)
HR3C
581 (1077)
356 (14)
254 (10)
CR30A
581 (1078)
152 (6)
102 (4)
The results were mixed but tend to imply that the wastage rates were slightly lower in
the platen section (test area 3) than in the pendant section (test area 2) for the same location, left to right in the boiler.
In two of the three spools (spools 10 and 25), the HR3C sample at the top exhibited
higher wastage rates, by a factor of 2.5 and 1.5 respectively, than the sample at the bottom, suggesting there may be a difference in the corrosiveness of the environment from
top to bottom [covering a span of approximately 0.9 m (3 ft)]. However, the wall loss in
the vertical legs of the HR3C tubes 19 and 20 near the top bends was similar to the loss
displayed by the bottom HR3C sample in spool 25. This may indicate that the wastage
rates are quite variable. An interesting observation was the difference in appearance
between the vertical and horizontal legs of tubes 19 and 20. While the vertical legs of
both tubes exhibited wall loss similar to that of the bottom HR3C sample, the horizontal
leg suffered little, if any, wastage. This orientation effect suggests a corrosion/erosion
mechanism caused by flyash-laden flue gas flowing across the vertical tubes.
As shown in Figures 5-54 and 5-55, increasing chromium content improved the corrosion resistance of the alloys. This is not an unexpected trend. In all but one case (i.e.,
spool 10), the CR30A material, which contains the highest chromium level of the materials listed (not counting the chromized layer in the T22 sleeve sections), exhibited the
lowest wastage rates. Unfortunately, at the most corrosive locations (spools 40 and 25
6-3

Discussion
in test area 2), none of the alloys displayed acceptable corrosion resistance. Fortunately,
however, the total area which exhibited unacceptably high corrosion rates was small,
and, for most of the reheater, the selected alloy, HR3C, performed well.
Chromized coatings were exposed only in test area 3. At best, the chromized layer offered temporary protection to the underlying T22 base material. As indicated in Figure
5-55, the intrinsic wastage rate of the chromized T22 samples was almost as low as that
of the CR30A, the best material. However, as indicated in Figure 5-46, the chromized
layer had disappeared in section 1 [average metal temperature of 585C (1085F)], and
significant attack of the T22 material had occurred. Attack of the layer with penetration
in localized areas to the T22 material was apparent in sections 2 and 3 [average metal
temperatures 554 and 522C (1029 and 972F), respectively]. It is expected that with
additional exposure time, the T22 material in these sections would have corroded at a
higher rate than all of the other materials tested. Since it is not known when the
chromized layer in section 1 disappeared, wastage rates of the chromized layer and T22
material independent of each other cannot be determined. This would also be the case
in the localized areas of section 2 where the layer was completely missing. Using an
original thickness of 0.33 mm (0.013 in.) for the chromized layer, the initial wastage rate
of the layer on section 3 is 64 py (2.5 mpy). However, this rate will increase with additional exposure time as the chromium content of the protective layer decreases away
from the surface.
The corrosion rate data obtained from the EPRI and ORNL probes exposed from September 1987 through October 1990 and November 1994 through February 1997, respectively, are plotted in Figure 5-58 for the alloys that were common to the three studies.
At first glance, the data show that, with the exception of the Type 347 alloy, the corrosion rates of the specimens on the retractable probes were in relatively good agreement
with each other, but were significantly less than those for the specimens that were in the
same temperature range in this study. However, in the temperature range at which the
comparisons are made, the rates of retractable probe specimens are being compared to
the rates of the first sleeve section (i.e., the section that was operating at the highest
temperature). Since the specimens in these two cases were at different locations (i.e.,
the sleeves were in test area 3 and in line with spool 25, whereas the retractable probes
were close to spool 10 in test area 2) and because location has been shown to be an
important variable, any comparison must take this into account. Nevertheless, since the
specimens on spool 10 exhibited the lowest corrosion rates, it is not surprising that the
rates for the retractable probe specimens, which were in the same approximate zone as
spool 10, were lower. When the corrosion rates of the retractable probe specimens are
compared to the rates of the specimens on spool 10, the values are very similar, in spite
of the fact that the specimens on the retractable probe were operating 56-111C (100200F) hotter. The corrosion rates for the various specimens used in the comparison are
reported in Table 6.2. Another interesting observation is that there is very little
difference in the wastage found in the EPRI and ORNL probes, despite the fact that the
alloys exposed were carburized in the latter and not in the former. On this basis, it
6-4

Discussion
might be concluded that the use of low-NOx burners did not adversely affect reheater
corrosion, at least not in this boiler.
In summary, the results of this program indicate that if superheater/reheater tubes are
exposed to operating conditions favorable for coal-ash corrosion, the boiler location, in
addition to tube metal temperature, is a key variable that affects the wastage rate. The
exact parameters governing the aggressiveness of the location are not known but are
believed to include the velocity and temperature of the flue gas, the heat flux, and the
ash deposition rate. In addition, since the samples operated close to the tube metal
temperatures expected in an advanced ultra-supercritical power plant, some information regarding tube material selection can be gleaned. While the data show that there
are alloys which will give a reasonable life in many areas, there are a limited number of
zones where none of the alloys tested will have adequate life. At these locations, shields
or the use of 40- to 50-percent chromium weld overlays may be needed. However,
because the number of highly corroded areas was small, it is believed that for most
boilers and most fuels, the results of this program provide sufficient data to select
superheater and reheater alloys for ultra-supercritical power plants.
6-5

Discussion
Table 6-2
Wastage Rates of Alloys Exposed on EPRI/ORNL Probes and Sleeve/Spool Sections
Alloy
EPRI Probe
ORNL Probe
Sleeve Section 1
Spool 10
MMW
[py (mpy)]
Temperature
[C.(F)]
MMW
[py (mpy)]
Temperature
[C (F)]
MMW
[py (mpy)]
Temperature
[C (F)]
MMW
[py (mpy)]
Temperature
[C (F)]
51 (2)
677-704
(1250-1300)
145 (5.7)
302 (11.9)
629 (1165)
691 (1275)
465-643
(18.3-25.3)
639 (1182)
165 (6.5)
581 (1077)
127-203 (5-8)
677-704
(1250-1300)
119 (4.7)
107 (4.2)
677 (1250)
723 (1334)
419 (16.5)
657 (1214)
178 (7)
573 (1064)
NF709
---
---
135 (5.3)
150 (5.9)
636 (1177)
684 (1284)
389-368
(15.3-16)
632 (1170)
89-114
(3.5-4.5)
584 (1084)
HR3C
76 (3)
677-704
(1250-1300)
97 (3.8)
13(0.5)
648 (1198)
703 (1297)
218-368
(8.6-14.5)
685 (1265)
54 (2.12)
566-588
(1051-1091)
CR30A
51 (2)
677-704
(1250-1300)
---
---
91-160
(3.6-6.3)
598 (1109)
76-89 (3-3.5)
581 (1077)
347
800H
6-6
7
CONCLUSIONS
Pressurized samples of various alloys considered for use in improved coal-fired

power plants were exposed for up to 45,004 hours in the reheater of TVA Gallatin
unit 2 without any forced outages caused by corrosion-induced wastage of the
samples/tubes. The exposure of up to seven alloys on multiple test sections produced corrosion data over a wide temperature band [521 to 685C (970 to 1265F)]
and at three different locations in the reheater. This temperature band covers the
expected tube-metal temperatures for an ultra-supercritical steam plant.
Based on the pitted and pockmarked appearance of the corroded surfaces and the
identification of potassium-iron-trisulfate in the ash deposits, wastage of the specimens was attributed, in part, to liquid-phase (coal-ash) corrosion. The presence of
internal carburized zones in all of the specimens (i.e., from test areas 2 and 3) indicates carbon carryover to the reheater and the existence of substoichiometric conditions below the deposits. No conclusion as to whether or not the bulk flue gas was
reducing could be made.
The relationship between coal-ash corrosion and temperature was found for many
of the alloys to follow the classical bell-shaped curve with the width and peak occurring at different temperatures for different alloys The alloys which did not show
the bell-shaped curve may not have been tested over a wide enough temperature
range.
For each alloy, location in the reheater was an important variable that affected the
wastage rate. There was a significant variation in wastage rates across the width of
the reheater and only a minor change between test areas 2 and 3 in the center of the
reheater. Although some of the variation across the width can be explained by differences in specimen temperature, other variables (e.g., composition and velocity of
flue gas and flyash content and composition) may have also been a factor. Erosion
from flyash-laden flue gas appears to have been a variable that had a contributing
role in the variation of wastage, indicating that corrosion/erosion was the primary
wastage mechanism in the specimens on spools 40 and 25, as well as those on the
sleeves. The low corrosion rates (based on ultrasonic thickness data only) for test
area 1, which had the highest steam temperature and lowest flue gas temperature,
could be due to a less corrosive combination of flue gas and ash deposits at this
7-1

Conclusions
location or the result of the specimen temperatures correlating with the downward
side of the bell-shaped curve in combination with a location/flue gas effect.
As expected, increasing chromium content improved the corrosion resistance of the

alloys. Unfortunately, at the worst location (spools 40 and 25 in test area 2), none of
the alloys exhibited acceptable corrosion resistance. Chromizing, which was used
solely in test area 3, offered only temporary protection to the underlying T22 material. The 0.33-mm (0.013-in.)-thick layer on sleeve section 1 [average metal temperature of 585C (1085F) had been consumed sometime during the 45,004-hour exposure period, resulting in significant attack of the T22 base metal.
Except for a few locations in test area 2, the main alloy, HR3C, showed acceptable
corrosion losses throughout the reheater. At the worst locations, approximately 20
to 30 tube sections about 3 m (10 ft) long had corrosion rates exceeding 250 py (10
mpy).
7-2
8
REFERENCES
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References
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8-3

Superheater Corrosion in USC Power Plant

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Superheater Corrosion in USC Power Plant

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SINGLE USER LICENSE AGREEMENT

Superheater Corrosion in UltraSupercritical Power Plants

Final Report, February 1999

EPRI Project Manager

DISCLAIMER OF WARRANTIES AND LIMITATION OF LIABILITIES

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The SO3 concentration formed by heterogeneous reaction on cooled surfaces is variable.

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The composition of the corrosive deposits changes with time.

The temperatures are not constant.

As part of RP1403-19, Boiler R&D for Improved Coal-Fired Power Plantssponsored

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range ([600-700C (1112-1292F)] where molten alkali-iron-trisulfates are stable. As the

MMW [py (mpy)]

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1 INTRODUCTION ................................................................................................................. 1-1

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Figure 5-51 Maximum metal wastage of section 1 specimens on sleeves............................ 5-63

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Acid Soluble, ppm(w)

K2O (as Na2O

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Low flue gas temperature in this area

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Wall thickness measurements (micrometer)

Metallurgical evaluation (microscopic and SEM/EDX)

Determination of wastage rates.

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