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Managing Steam-Side Oxidation

and Exfoliation in USC Boiler Tubes
J.P.
Shingledecker*
Electric Power
Research Institute,
Charlotte, N.C.

B.A. Pint*
and A.S. Sabau
Oak Ridge National
Laboratory,
Oak Ridge, Tenn.

A.T. Fry
National Physical
Laboratory,
Teddington, UK

I.G. Wright
Wright HT,
Denver, Colo.

Materials are
the key
enabling
technology
driving
development of
high-efficiency
power plants,
which requires
better
fundamental
and practical
understanding
of the effects
of operating
environments.

*Member of ASM
International

uperheaters (SH) and reheaters (RH) in

modern supercritical (SC) and ultrasupercritical (USC) coal-fired steam
power plants operate with maximum steam
temperatures between 580 and 620C and pressures up to 28 MPa. A single unit can contain
miles of tubing, therefore the formation
(growth) of steam-grown oxide scales on the inside of this tubing and the potential for these
scales to exfoliate during operation can have a
significant impact on plant operations. In 2012,
National Physical Laboratory (NPL) and Electric Power Research Institute (EPRI) held a joint
workshop to review recent experience in the
practical management of exfoliation, progress
in understanding the phenomenon, and development of models intended to provide the basis
for improved approaches. This article briefly
describes some of the characteristics of oxide
growth and exfoliation, the impact of these oxides in modern power plants, and highlights
findings from the workshop and requirements
for additional research.
Oxide growth
The growth and exfoliation of thermally
grown oxides, or scales, in steam is a complex
phenomenon that depends on alloy composition, microstructure (including surface condition), temperature, pressure, and plant
operation. Steels and stainless steels used in SH
and RH tubing have varying chemical compositions with 2 to 25 wt% chromium and 0 to 25%
nickel, and can be austenitic, bainitic, or
martensitic.
Figure 1 shows the difference in oxide scale
morphology between martensitic T91 alloy
steel (9Cr-1Mo-V) and austenitic TP347H
stainless steel (18Cr-8Ni-Nb) after service in
the superheaters of utility steam boilers. Scale
on T91 forms as layers of uniform thickness,
and separation occurs between the main inner
and outer layers (with the outer layer lifting
off ). The inner layer of the essentially doublelayer scale formed on TP347H has a very irregular thickness, and while separation also occurs
between the two main layers, the outer layer exfoliates completely. Figure 2 shows the complexity in the types of oxides and defects that
can form in a 9% Cr martensitic steel.

Results of exfoliation
When oxide scales fail (crack), separate, and

Epoxy

Scale

Alloy: T91

50 mm
As polished

50 mm

TP347H

Fig. 1 Structures of oxide scales (polished cross

sections) observed on T91 alloy steel after about
eight years of service at a steam temperature of
approximately 541C, and on TP347H stainless
steel after about six months service in steam at a
temperature of approximately 580C. Alloy
composition plays an important role in the
structure/morphology of the oxide scale.
Ni coating
Fe2O3
Fe3O4

Voids gap

(Fe,Cr)3O4 + Fe3O4

Alloy

FeO + Cr2O3

100 mm

Fig. 2 Cross section of 9% Cr steel after

laboratory exposure for 10,000 hours in dry steam
at a temperature of 625C showing the complexity
of the oxide scale.

are lost (exfoliate) from tube surfaces, there is

potential for tube overheating (thermal insulation from a lifted scale), tube blockage from accumulation of oxides, and erosion damage to
downstream components. Figure 3a shows a
tube blocked from oxides that accumulated in
the lower loop of a superheater after a plant
shutdown. The blockage severely restricted
steam flow and caused a short-term overheat
tube failure during the unit restart. The figure

ADVANCED MATERIALS & PROCESSES JANUARY 2013

23

(a)

(b)

Fig. 3 Tube blockage (a) and erosion damage to a valve stem (b), both
due to the presence of exfoliated steam-grown oxides in utility boilers.

also shows erosion damage to a valve stem due to exfoliated oxides. A 2011 EPRI survey of U.S. utilities showed
that over 50% of respondents experienced exfoliation-related damage in their power plants including tube failures,
erosion of drain lines, reduced steam turbine performance
due to erosion of blading, and increased maintenance of
valve components.
Modeling the process
To minimize the likelihood of tube failures, manage
exfoliation, and select suitable materials for different
operating conditions, EPRI conducted modeling work
on the process of oxide growth and exfoliation taking
into consideration the accumulation of strain in the
oxide or oxide layers[1]. Strain accumulates during operational transients, and is a function of many factors in7th International Conference on
Advances in Materials Technology
for Fossil Power Plants
October 22-25, 2013
Hilton Waikoloa Village, Hawaii
Materials are the key enabling technology that drives the development
of high-efficiency power plants. To effectively achieve desired life, manage high-temperature degradation, and select proper materials for demanding high-temperature, high-pressure, and corrosive conditions,
improved fundamental and practical understanding is needed. EPRI supports and sponsors expert workshops, projects, and large group projects
to address key industry needs in many of these areas. This conference
brings many of these individuals, organizations, and EPRI collaborators
together to review the most recent advancements and help shape future research.
This conference is the 7th in a series of conferences on the subject of
materials for advanced plants held every three years by EPRI. It is intended to continue the promotion of information exchange between scientists and engineers on an international scale. Invited keynote speeches
by prominent scientists, as well as submitted papers, will be presented.
Conference participants are likely to represent domestic and international utilities, equipment manufacturers, alloy materials vendors, forge
shops, casting houses, universities, national laboratories, and consulting/research organizations. For more details on the conference, visit the
calendar of events on www.epri.com.
EPRI teamed with ASM International to publishing proceedings of the
4th, 5th, and 6th conferences, and will collaborate again to publish proceedings of this 7th conference.

24

ADVANCED MATERIALS & PROCESSES JANUARY 2013

Mean coefficient of thermal expansion (a), x10-6 C-1

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Fe3O4
TP347

20
FeCr
spinel
16

Fe2O3

12

8
0

200

400

600 800 000

Temperature, C

1200 1400

Fig. 4 Coefficient of thermal expansion of various iron oxides

compared with that of TP347H stainless steel[4].

cluding scale chemistry and structure, physical properties of the scale, oxide growth stresses, creep, and physical tube dimensions. One major driver for strain
accumulation and eventual scale failure is the mismatch
in coefficient of thermal expansion (CTE) between
oxide layers and substrate alloys. Figure 4 shows the
CTE as a function of temperature for various iron oxides compared with TP347 stainless steel.
Modeling oxide growth and strain accumulation
(which is particularly high during unit start-up and shutdown events) enables identification of the point when
oxide exfoliation is expected to occur. Applying this
methodology to the operation of a superheater (including temperature and heat-flux gradients) can provide
guidance on the amount of scale lost by exfoliation and
the potential for tube blockage. Figure 5 shows modeling results for a stainless steel superheater. Tube blockage is predicted during the first two to three years of
operation (8000 to 20,000 hours), and the likelihood of
further blockages decreases with time assuming that exfoliated scale is removed after each shutdown event (i.e.,
the scale is blown through the system), which is consistent with field experience.
EPRI-NPL workshop findings
Challenges with steam-side oxide growth and exfoliation management are being experienced worldwide, and
an experts workshop was held at NPL in January 2012[2]
to bring together practical experience and current research
to identify key knowledge gaps and research needs. A
number of issues were identified including:
Boilers with nominally the same materials and
operating conditions had vastly different experiences
with exfoliation, and the role of boiler design has not
been clearly identified.

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New research
Work also continues through the use of advanced characterization techniques to further clarify mechanisms and
long-term stability of steam-grown oxides scales. Figure 6
shows an electron probe secondary electron image and a
color compilation of Fe, Cr, and O x-ray maps from the
inner scale formed on a stainless steel superheater after
~3.5 years of service in a SC steam boiler. The formation of
a chromium rich scale is expected to slow the oxide growth
rate significantly, but the x-ray map clearly indicates regions of oxide where no Cr-rich oxide layer has formed adjacent to the metal and regions in the metal with
chromium depletion. Typically, a uniform Cr-rich layer is
present at the reaction front, and this result suggests there
is nonuniform growth, perhaps initiated by Cr depletion.
Measurements of these various layers with time will provide a more detailed picture of the reaction mechanism
during long-term service in supercritical steam.
References
1. A.S. Sabau, I.G. Wright, and J.P. Shingledecker, Oxide scale
exfoliation and regrowth in TP347H superheater tubes, Materials and Corrosion, 63 (10), p 896908, 2012.
2. Second EPRI-NPL Workshop on Scale Exfoliation From
Steam-Touched Surfaces, Proc. Workshop held at Bushy
House, National Physical Laboratory, Teddington, London,
January 17-18, 2012; EPRI, Palo Alto, Calif.: 1026663.
3. B.A. Pint, J.P. Shingledecker, and I.G. Wright, Characterization of Steam Oxidation Products from Field-Exposed Tubes,
in Advances in Condition and Remaining Life Assessment for
Fossil Power Plants, EPRI, Charlotte, N.C., presented Hilton
Head, S.C., Oct. 2012.
4. S.J. Osgerby and L.N. McCartney, Steam oxidation of 912Cr martensitic steels: characterisation and modeling the

1
Predicted blocked area fraction

In the case of modeling, the failure criteria for

exfoliation need further refinement, and scale defect
sizes that are key to developing failure criteria are
currently unknown.
Many discrepancies exist between laboratory test
results and those obtained from field experience. This
is partly due to difficulties in simulating some key
aspects of plant operation in laboratory testing, and
to the fact that mass gain and not oxide thickness are
often reported from laboratory examinations. This is
critical because laboratory testing is currently being
used to validate materials for future highertemperature advanced USC steam designs.
There may be a need to define temperature use
limits for alloys based not only on high-temperature
strength, but also on exfoliation considerations.
Based on this feedback, a major outcome of the workshop was the need for development of an atlas of steamgrown oxide structures containing the necessary details to
provide practical diagnostic guidance to power-plant operators dealing with oxide exfoliation, a consistent set of data
to use for modeling activities, and accepted field microstructures for laboratory researchers to validate their
experimental approaches. EPRI and Oak Ridge National
Laboratory have started this effort[3].

Outlet steam temperature, C

0.8

0.6

0.4
Porosity of deposit
= 25%
0.2

10,000

20,000
Time, h

30,000

40,000

Fig. 5 EPRI modeling results for exfoliation blockage in a stainless steel

superheater, assuming six-month (~4000 h) operational cycles and
assuming removal of all exfoliated scale after each shut-down event (shown
by data points). The propensity for tube blockage decreases after two years
of operation, which is consistent with industry experience.
Epoxy

Inner oxide

347H
29,672 h at 582oC

10 mm

Fig. 6
Secondary
electron
image (top)
and
characteristic
x-ray images
(bottom) for
Fe, Cr, and O
in an oxide
formed on a
stainless steel
superheater
tube. Regions
of Cr
enrichment
(light blue)
and depletion
(red) are
observed.

Cr-depleted alloy

10 mm

Cr-rich oxide

spalling of oxide scale, Materials for Advanced Power Engineering, 21, p 1169-1179, 2002.
For more information: John Shingledecker, Ph.D., is senior
project manager, Fossil Materials & Repair Program (P87),
Electric Power Research Institute (EPRI), Charlotte, N.C.,
tel: 704/595-2619; email: jshingledecker@epri.com; www.epri.
com.
ADVANCED MATERIALS & PROCESSES JANUARY 2013

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