Proceedings of

2000 International Joint Power Generation Conference

Miami Beach, Florida, July 23-26, 2000

IJPGC2000-15049

MATERIALS FOR BOILERS IN ULTRA SUPERCRITICAL POWER PLANTS

R. Viswanathan/EPRI W. T. Bakker/EPRI

ABSTRACT can be achieved by increasing steam temperature and pressure

The efficiency of conventional boiler/steam turbine fossil by use of advanced steam conditions(1). For example, using a
power plants is a strong function of the steam temperature and 538°C/18.5 MPa (1000°F/2600 psi) steam plant as a base case,
pressure. Research to increase both has been pursued an efficiency increase of nearly 6% is achieved by changing the
worldwide, since the energy crisis in the 1970s. The need to steam conditions to about 593°C/30 MPa (1100°F, 4300 psi).
reduce CO2 emission has recently provided an additional At 650°C (1200°F) the increase in efficiency is as much as 8%.
incentive to increase efficiency. Thus, steam temperatures of The desire for increased efficiency led eventually in the late
the most efficient fossil power plants are now in the 600°C fifties and early sixties to the introduction of numerous
(1112°F) range, which represents an increase of about 60°C supercritical boilers operating at or above 565°C (1050°F) and
(108°F) in 30 years. It is expected that steam temperatures will 24 MPa (3400 psi) steam pressure. The more famous ones
rise another 50-100°C (90-180°F) in the next 30 years. The representing extreme conditions among these include a 375
main enabling technology is the development of stronger high MW plant Drakelow C in UK, a 125 MW plant, Philo 6, owned
temperature materials, capable of operating under high stresses and operated by Ohio Power Co. since 1957 and the Eddystone
at ever increasing temperatures. Recently EPRI performed a 1 plant owned and operated by the Philadelphia Electric Co.
state-of-the-art review of materials technology for advanced since 1959. Philo 6 has been operational under design steam
boiler/steam turbine power plants (ultra supercritical power conditions of 31 MPa (4500 psi) and a 610/565/538°C
plants). The results of the review show that high strength (1150/1050/1000°F) double re-heat temperature cycle.
ferritic 9-12Cr steels for use in thick section components are Eddystone 1 was designed to operate under steam
now commercially available for temperatures up to 620°C conditions of 34.5 MPa (5000 psi) and 650/565/565°C
(1150°F). Initial data on 2 experimental 12Cr ferritic steels (1200/1050/1050°F), and has been operational since 1959. The
indicate that they may be capable of long term service up to plant has operated under de-rated conditions of 32.4 MPa (4700
650°C (1112°F), but more data are required to confirm this. psi) and 605°C (1125°F) for most of its service life, because of
Advanced austenitic stainless steels for use as super- and mechanical and metallurgical problems. Most of the problems
reheater tubing are available for service temperatures up to were due to the use of austenitic steels for heavy section
650°C (1112°F) and possibly 700°C (1292°F). None of these components operating at high temperatures. These steels have
steels have been approved by the ASME Boiler Code Group so low thermal conductivity and high thermal expansion resulting
far. Higher strength materials are needed for upper water walls in high thermal stresses and fatigue cracking. These problems
of boilers with steam pressure above 24 MPa (3400 psi). A and the general low availability of many supercritical plant due
high strength 2-1/2%Cr steel recently ASME code approved as to “teething” problems temporarily dampened utility interest in
T-23 is the preferred candidate material for this application. building super or ultra supercritical plants and consequently
Field trials are in progress. This paper will present the results most utilities reverted back to plants with subcritical conditions
of the EPRI review in detail, relating to boiler material. of about 525°C (1000°F) and 17 MPa (2600 psi).
The energy crisis in mid 70s and subsequent sharp increase
in fuel prices re-kindled interest in the development of more
INTRODUCTION AND BACKGROUND efficient P.C. power stations. EPRI initiated a study of the
The goal of improving the efficiency of pulverised coal development of more economic coal-fired power plant in
(PC) power plants, by increasing the temperature and pressure 1978(2,3). This study led to a number of research and
of the working fluid (steam) has been pursued for many development activities involving US, Japanese and European
decades. Figure 1 illustrates the improvements in heat rate that

1 Copyright © 2000 by ASME

manufacturers. These activities focused on developing further headers, superheater tubing and waterwall tubing. All of them
the existing high-temperature-resistant ferritic-martensitic 9%Cr have to meet creep strength requirements. In addition, pipes
and 12%CrMoV steels for the production of rotors, casings and and headers, being heavy section components, are subject to
chests, pipes and headers capable of operating at inlet steam fatigue induced by thermal stresses. Ferritic/martensitic steels
temperatures of up to 650°C (1200°F). One of the early are preferred because of their lower coefficient of thermal
conclusions from this project was that the construction of a expansion and higher thermal conductivity compared to
plant with a 593°C (1100°F)/31 MPa (4500 psi) steam austenitic steels. Many of the early problems in the USC plants
condition would be feasible with only minor evolutionary were traceable to the use of austenitic steels which were very
improvements in materials technology. This has in fact proved prone to thermal fatigue. Research during the last decade has,
to be correct as evidenced by the spate of power plants built in therefore, focused on developing cost-effective, high-strength
Japan and Europe over the last decade. In Japan, nearly 16 ferritic steels that could be used in place of austenitic steels.
plants, most of them with typical main steam temperature of This has resulted in ferritic steels capable of operating at metal
about 593°C (1100°F) and pressure of 24 MPa (3400 psi) are temperatures up to 620°C (1150°F), with good weldability and
operational. In Europe, nearly a dozen plants are operational fracture toughness.
with main steam temperature/pressure of 583°C (1080°F)/30 Superheater and reheater (SH/RH) tubing application calls
MPa (4200 psi). for high creep strength, thermal fatigue strength, weldability,
An improvement in thermal efficiency of the plant not only resistance to fireside corrosion/erosion and resistance to
reduces the fuel costs but also reduces the release of SO2 NOx steamside oxidation and spallation. Thermal fatigue resistance
and CO2 emissions. The latter is very significant in view of the as well as cost considerations would dictate the use of
world-wide agreements to reduce CO2 emissions by 2010 and ferritic/martensitic steels. Unfortunately, the strongest of these
the fact that a 1% increase in efficiency of an 800 MW machine steels which can be used up to metal temperature of 620°C
would lead to a life-time reduction in CO2 approaching one (1150°F)1 purely from a creep strength point of view are still
million tonnes(4). These environmental factors have provided an limited by fireside corrosion to metal temperature of 593°C
added incentive to building USC plants in recent years. (1100°F). This corresponds to a steam temperature of about
A major challenge in constructing USC plants has been in 565°C since SH/RH metal temperature can exceed the steam
the area of materials technology. While materials suitable for temperature by as much as 28°C (50°F). Excessive corrosion of
metal temperatures up to 565°C (1050°F) were available, even ferritic steels caused by liquid iron-alkali sulfates in the tube
20 years ago, further developments were needed to achieve deposits is an acute concern in the USA, where high sulfur
593°C (1100°F) and beyond. Intense R&D efforts were carried corrosive coals are used more frequently than elsewhere.
out in Japan, USA and Europe. In each case, a phased approach Therefore high strength ferritic stainless steels such as T-91 are
was adopted. For instance, in the USA, the phases 0 to 2 were infrequently used in the U.S. The standard practice is to use T-
defined as shown in Table 1, where the temperatures given are 22 for the lower temperatures and SS304H or SS347 for the
for the main steam and first and second reheats. highest temperatures.
The Phase 0 conditions were considered to be achievable With respect to waterwall tubing, the concern is twofold.
with the state-of-the-art technology in 1978 while the Phase 1 High supercritical pressures and the use of high heat release
conditions were considered to be achievable with only minor furnaces will increase the waterwall temperatures to the point
improvements. The technology needed for phase 2 was that easily weldable low alloy steels such as T-112 (1.25Cr,
considered well beyond reach and hence, an intermediate goal 0.5Mo) have insufficient creep strength. Higher strength steels
of 620-630°C (1150-1166)/30 MPa (4200 psi) seems to have such as T-91* are available, but require postweld heat
been established in Europe and Japan. For convenience, this treatments. The second concern is corrosion. Recent results in
Phase will be referred to as 1B in this paper. Although the the USA on boilers retrofitted with low NOx burner systems,
material developments for Phase 2 have not been fully using overfire air, indicate that the present low alloy steels can
achieved, technology exists today that will enable building suffer from excessive corrosion, as high as 2 mm/yr. Weldable
plants that can meet Phase 1B conditions. This has been made high strength alloys clad or overlaid with high Cr alloys have to
possible by some very exciting progress in developing highly be utilized to reduce or eliminate excessive corrosion(6).
creep resistant 9 to 12%Cr ferritic steels. The objective of this
report is to review developments in materials technology related
to boilers. A similar review of turbine materials will be
presented elsewhere. A complete and more detailed review of
materials for all plant components may be found in Reference 5.
1
All temperatures cite in the paper are steam temperatures unless
otherwise specified. For header and piping, metal temperature is nearly equal
2.0 BOILER MATERIALS REQUIREMENTS
to the steam temperature. For tubing, the metal temperature is generally higher
The key components whose performance is critical for ultra than the steam temperature by up to 28°C (50°F).
supercritical (USC) plants are high-pressure steam piping and 2
ASME boiler code steel designation, equivalent pipe steels are
designated as P-11, 92, etc., while forgings are designated F-11, 91, etc.

2 Copyright © 2000 by ASME

2.1 Historical Evolution of Steels primarily solid solution strengtheners. V and Nb contribute to
Masuyama has presented an excellent historical perspective precipitation strengthening by forming fine and coherent
on the development of steels for power plants as shown in precipitation of M(C, N)X carbonitrides in the ferrite matrix.
Figure 2(7). The figure shows 105h creep rupture strength at Vanadium also precipitates as VN during tempering or during
600°C (1112°F) by year of development. They classify the creep. The two elements are more effective in combination at
ferritic steel development in terms of 4 generations as shown in levels of about 0.25%V and 0.05%Nb. Chromium contributes
Table 2. to solid solution strength as well as to oxidation and corrosion
In the field of austenitic steels, efforts were made from the resistance. Nickel improves the toughness but at the expense of
1970’s to the early 1980’s to improve conventional 18Cr-8Ni creep strength. Partial replacement of Ni by Cu helps stabilize
series steels originally developed as corrosion resistant the creep strength. Carbon is required to form fine carbide
materials for chemical use, mainly with respect to their creep precipitates but the amount needs to be optimized for good
strength. Another goal pursued from the 1980’s to the early weldability.
1990’s was to improve the creep strength of conventional 20- Atom probe results have shown that boron enters the
25Cr series steels having superior oxidation and corrosion structure of M23C6 and boron segregates to M23C6 - matrix
resistance. interface(8). It has also been suggested that boron helps reduce
coarsening of M23C6 and that boron also assists in nucleation of
2.1.1 Evolution of Ferritic Steels VN, the mechanism of “latent creep resistance (8).
Ferritic steel developments are mostly aimed at their use Cobalt is an austenite stabilizer and developers of NF12
for thick section pipes and headers. Table 3 shows the chemical suggest that is why they used cobalt additions (8). Cobalt is
compositions of ferritic steels for power boilers. The systematic known to delay recovery on tempering of martensitic steels.
evolution of these steels has been thoroughly reviewed by Cobalt also promotes nucleation of finer secondary carbides on
Masuyama, as shown in Figure 3(7). Among the 9%Cr steels tempering. This is attributed both to its effect on recovery and
fully commercialized, the P91 steel has the highest allowable its effect on the activity of carbon (8). Cobalt also slows
stress and has been extensively used all over the world as a coarsening of alloy carbides in secondary hardening steels.
material for headers and steam pipes in ultra supercritical plants This was suggested to be the result of cobalt increasing the
operating at steam temperatures up to 593°C (1100°F). Alloy activity of carbon and cobalt not being soluble in alloy carbides.
NF616 (P-92), developed by substituting part of the Mo in P91 Results of Hidaka suggest that Co has a positive effect on creep
by W, has an even higher allowable stress and can be operated rupture stress.
up to steam temperatures of 620°C (1150°F). E911 is a
European alloy similar in composition to NF616 with similar 2.1.2 Evolution of Austenitic Steels
capabilities. Beyond 620°C (1150°F), the 9%Cr steels become Austenitic steels are candidates primarily in the finishing
limited by oxidation resistance and 12%Cr steel and austenitic stages of superheater/reheater tubing, where, oxidation
steels have to be used. resistance and fireside corrosion become important in addition
Among the 12%Cr steels, HT91 has been widely used for to creep strength. From a creep strength point of view, T91 is
tubing, headers and piping in Europe. Use of the steel in Japan limited to 565°C steam (metal 593°C) and NF616, HCM12A
and US has been limited due to its poor weldability. HCM12 is and E911 are limited to 593°C steam (metal 620°C). Even the
an improved version of HT91 with 1% W and 1% Mo, having a strongest ferritic steel today is limited to 593°C (1150°F) (metal
duplex structure of δ-ferrite and tempered martensite with temperature) from an oxidation point of view. At temperatures
improved weldability and creep strength. Further increases in above these, austenitic steels are required. Hence there has
creep strength by substituting more of the Mo with W and been considerable development with respect to austenitic
addition of Cu has resulted in alloy HCM12A (P-122), which stainless steels. In actual practice in the U.S. SS304M and
can be used for header and piping up to 620°C (1150°F). Two SS347 are widely used instead of T-91 in superheater
alloys NF12 and SAVE12 having an even higher creep strength applications, mainly because they are easier to weld, while the
than HCM12A are in the developmental stage. NF12 contains cost difference is relatively small.
2.5%Co, 2.6%W and slightly higher B compared to HCM12A. Table 4 lists the compositions of various stainless steels for
SAVE12 contains 3% Co, 3% W, and minor amounts of Ta and SH/RH tube applications. The steels fall into four categories:
Nb. These latter elements contribute to strengthening by 15Cr, 18Cr, 20-25Cr and higher Cr stainless steels. The various
producing fine and stable nitride precipitates. HCM2S (T-23) a stages in the evolution of these steels have consisted of initially
low carbon 2-1/4Cr-1.6W steel with V and Nb is a cost- adding Ti and Nb to stabilize the steels from a corrosion point
effective steel with higher creep strength than T22. Because of of view, then reducing the Ti and Nb content (understabilizing)
its excellent weldability without pre- or post-weld heat to promote creep strength rather than corrosion, followed by Cu
treatment it is a good candidate for waterwall tubing. additions for increased precipitation strengthening by fine
The role of alloying elements in development of the ferritic precipitation of a Cu rich phase. Further trends have included
steels has been extensively investigated. W and Mo and Co are austenite stabilization using 0.2% nitrogen and W addition for

3 Copyright © 2000 by ASME

solid solution strengthening. This development sequence is reported when the material has been given inadequate solution
illustrated in Figure 4(7). heat treatment. Due to these concerns, these alloys have not
found much favor in the United States, the United Kingdom, or
2.2 Choice of Materials for Headers and Steam Pipes Japan. Alloys with improved weldability characteristics, such
A summary of candidate ferritic steels for thick section as HCM12M have been adequately characterized for tubing and
applications at various temperatures in shown in Table 5. large-diameter, thick-wall pipes.
Material-property requirements for headers and steam pipes are With regard to the 9Cr-2Mo steel (HCM9M), the feasibility
likely to be similar, and hence they have been grouped together. of fabrication of large-diameter, thick-wall piping and
Some minor differences exist which may affect material application to in-plant header and main steam piping was first
selection. The steam temperature is likely to be much more demonstrated in 1985(10). The practical use of this material has
uniform in steam pipes, but subject to time-dependent and been easy because its simple composition lends fabricability
location-dependent fluctuations in headers. Hence, the thermal- and weldability comparable to those of low-alloy steels. The
fatigue-strength requirements are greater for headers than for toughness of large-diameter pipes has been found to be over
steam pipes. Self-weight-induced stresses are less important for 102 J/cm2 (460 ft-lb/in.2) at 0°C (32°F). Allowable stresses are
headers than for steam pipes, permitting heavier-wall comparable to those for the HT9 alloy, but lower than those for
construction and an attendant higher temperature/pressure P91. Service experience of nearly 25 years have been
capability for a given material when used in headers. One of accumulated since the alloy was developed with about 2000
the most important differences is that headers have many tons having been produced specifically for SH/RH tubes and
welded attachments to inlet stub tubes from reheaters and steam pipes.
superheaters and intersections of outlet nozzles connecting The modified 9Cr alloy, P91, appears to be quite superior
pipework. Depending on the selection of materials for the to HT9, HT-91 and to HCM9M in terms of creep-rupture
superheater/reheater tubes and the header piping, dissimilar- strength and is, hence, the most promising candidate for use in
metal welded joints may be required. The integrity of such header and steam piping for temperatures up to 595°C
austenitic-to-ferritic welds when 9 to 12%Cr steels form the (1100°F). One of the early applications was by the Chubu
ferritic components needs to be more thoroughly investigated. Electric Power Company (Kawagoe Power Station, Units 1 and
Headers and pipes have traditionally been made from low 2) for 565°C (1050°F) steam conditions as headers and steam
alloy steels such as P11 and P22 in the USA. Even in pipes. A majority of the recent European supercritical plants
conventional boilers, such headers can fail due to thermal have utilized P91 as main steam and reheat piping. Numerous
fatigue cracking, caused by cycling. A common failure mode is retrofit applications have also been carried out for
the cracking of the ligaments between the tube boreholes(9). headers/steam pipes. The alloy was approved by the ASME
The use of higher temperatures and pressures can only increase Boiler Code Committee for various uses between 1983 and
the problem. Previous attempts to use austenitic steels have not 1986 as T, P, F-913. Since that time, the alloy has found
been successful due to high thermal expansion of these steels. applications worldwide and is available from many sources,
Several candidate ferritic steels have emerged succeeding since the composition is not proprietary. It is especially popular
the P11 and P22 steels, which are capable of operation up to in Europe, where it proved superior in creep strength as well as
593°C (1100°F). These include HT9, HT91, HCM9M, HCM12 weldability, compared to the well-known HT91 steel, used in
and P91. Alloys HT9 and HT91 are well-established steels with supercritical boilers.
an extensive stress-rupture database which exceeds 105 h at The high creep strength of grade 91 steel is due to small
temperatures in the range 500 to 600°C (930 to 1110°F) for all additions of V, Nb and nitrogen, which lead to the precipitation
product forms. There is also extensive operating experience of M23C6 carbides and (Nb, V) carbonitrides, in addition to
(>20 years) in Germany, Belgium, Holland, south Africa, and solution strengthening by Mo. Very extensive studies were
Scandinavia for steam temperatures up to 540°C (1000°F) and made world wide to evaluate the suitability of P-91 for heavy
some limited experience on a few small units with steam section components. These included manufacturing studies,
temperatures from 560 to 580°C (1040 to 1075°F). This welding trials, both similar and dissimilar, bending trials, both
experience generally has been satisfactory. Difficulties have, hot and cold, and various mechanical tests, on both virgin and
however, been reported during fabrication and particularly aged samples(11,12). The net result of all these tests is that P-91
during welding and post-weld heat treatment. This arises is now the preferred heavy section materials for supercritical
because the relatively high carbon content of the steel (0.2%) boilers worldwide. However, most designers feel the use of P-
and the correspondingly low MS temperature promote the 91 will probably be limited to steam conditions of about
possibility of austenite retention after welding, high residual 593°C/25 MPa. This is especially the case in Europe, where the
stresses, and cracking prior to and during stress relief. It is allowable creep strength is about 10% lower than in Japan and
reported that these problems have been overcome by careful the U.S.
control of preheat treatment and postweld heat treatment backed
up by vigorous quality control. Difficulties have also been
3
T = tubing, P = pipe, F = forging

4 Copyright © 2000 by ASME

 Fortunately, Professor Fujita in Japan discovered that the accelerated high-temperature conditions in a high-pressure cell
creep strength of 9-12Cr, Mo, V, Nb steels can be raised by operated by Mitsubishi Heavy Industries.
about 30% through partial substitution of Mo by W(13). This has Some additional design considerations in applying the
spawned another round of intensive alloy development and advanced ferritic steels are as follows:
evaluation worldwide(14). Two of these steels, a 9Cr steel 1. The high temperature strength of the advanced alloys,
developed by Nippon Steel NF616 (P-92) and a 12Cr steel e.g. NF616, HCM12A and E911 (P-92, P-122, E911) is
HCM12A developed by Sumitomo metals (P-122) have been essentially the same as that of austenitic alloys. But oxidation
approved for use in boiler heavy section components by ASME. resistance is less than that of austenitic alloys. This parameter
Another W containing steel E-911 is in advanced development of advanced 9 to 12Cr alloys must be more fully evaluated prior
in Europe. The allowable strength of the new steels at 600°C is to application to high temperature parts.
about 25% higher than that of P-91. Thus these steels should 2. Post weld heat treatment (PWHT) is always required
allow steam temperatures up to 620°C and pressures up to 34 for welded joints of advanced 9 to 12 Cr alloys to ensure
MPa. minimal stress and optimal ductility. Design must be made to
Figure 5 shows a plot of the allowable stress at various reduce field heat treatment as much as possible to keep
temperatures for ferritic steels(7). The figure clearly shows the production and PWHT costs minimal.
enormous advances in the materials technology which have 3. In the weldment of dissimilar alloys, material selection
been made in the last 20 years. Especially at the higher must be based on consideration of PWHT temperature. For
temperatures, the most advanced steels show allowable stresses example, the 9Cr-1Mo alloy and 1Cr-0.5Mo steel would not be
that are nearly 2.5 to 3 times that of the workhorse steel in acceptable materials for the case of joints in a longitudinal
conventional plants, i.e., 2-1/4Cr-1Mo steel (P22). The direction; measures must be taken to consider the behavior of
layering of the alloys into the different generations described welded joint creep rupture strength.
earlier is also evident. HCM12A (P122), NF616 (P92) and 4. Last but not least, is the apparent susceptibility of
E911 emerge as the three highest strength alloys suitable for ferritic steel welds to Type IV cracking, which occurs at the
ultra supercritical plants up to 620°C, followed by T91, edges of fine grained HAZ material adjacent to unaffected
HCM12, EM12, HCM9M and HT91 suitable for intermediate parent material. Susceptibility to this has been clearly
temperatures up to 593°C followed by T22 for use up to 565°C demonstrated for 1/2CrMoV, 2-1/4Cr-1Mo and 9Cr-1Mo (T91)
(1050°F). NF12 and SAVE12 are still developmental but are steels. Safety margins of 10 to 20% are sometimes adopted to
expected to meet the Phase 2 goals. This rationale has been provide for this mechanism. Since the problem in girth welds is
incorporated in the materials selection shown in Table 5. primarily associated with bending stresses, the problem can be
A very interesting fact is that application of the new steels overcome by proper plant design and maintenance. This issue
may actually result in a capital cost reduction. Figure 6 shows has therefore been generally glossed over.
the allowable design stresses and a comparison of the relative
wall thicknesses at various temperatures(15). At any given 2.3 Choice of Materials for Superheater/Reheater
temperature, higher allowable stresses for a material permits Tubes
design of thinner wall headers/pipes. This not only reduces The superheater tubes in the boiler are likely to undergo the
thermal stresses, but also reduces cost. From Figure 6, section most severe service conditions and must meet stringent
thicknesses and materials costs can be calculated as a function requirements with respect to fire-side corrosion, steamside
of temperature and pressure. Figure 7 shows the results for a oxidation, creep rupture strength and fabricability. In addition,
pressure of 31 MPa (4500 psi). The cost of using high strength they must be cost-effective. Based on these issues candidate
steel becomes lower than that of P-22 steel at about 520°C. The materials for various team conditioning have been summarised
cost of using the W containing steel is lower than that of P-91 in Table 5. The rationale for these selections is discussed in the
above about 550°C. These relations do not change very much following sections.
with decreasing pressure down to 20 MPa (3000 psi). Actual
fabricated and installed cost differences should be even larger 2.3.1 Creep Rupture Strength
as the thinner pipes need less welding and are easier to install. In terms of creep rupture strength, application of ferritic
Fewer supports are needed thus reducing costs further. steels for tubes follow the same logic as for the headers/pipes
A sample list of European installations using the most discussed earlier. Thus, tubes made of T22 should be limited to
advanced steels NF616 (P92), HCM12A (P122) and E911 is steam temperature of 538°C (1000°F); Alloys T91, HCM12,
shown in Table 6(15b). There is considerable interest in using EM12, HCM9M and HT91 limited to steam temperature of
these alloys for outlet headers and main steam and reheat pipe 565°C (1050°F); Alloys T-92, P-122 and E911 limited to steam
work. Full-scale headers have been being installed in a 415MW temperature of 593°C (1100°F). Under corrosive conditions
supercritical plant under consideration by the Danish utility, however, even the best ferritic steel may be limited to 563°C
ELSAM. Headers using P92 and P122 have been constructed (1050°F) temperature and austenitic steels are needed. Although
and installed. Two of the headers will be tested under the creep resistance of 9Cr steels is adequate for use at 593°C,

5 Copyright © 2000 by ASME

there is considerable doubt about their fireside oxidation are present, fine distinctions between ferritic steels may be
resistance. Thus 12Cr steels, such as P122 are preferred. academic, and it is usually necessary to use austenitic steels
In practice, the high Cr, high strength ferritics have found containing chromium in excess of 20%.
little use in the U.S. because of perceived welding problems. T- A ranking of the performance of various austenitic alloys in
22, SS304H and SS347 are the steels most commonly used in the presence of trisulfates has been provided by Ohtomo et al(20)
supercritical boilers (3500 psi) in the USA. on the basis of short-term laboratory tests (see Fig. 13). The
For convenience, austenitic steels can be classified as those plots of weight loss versus temperature exhibit a bell-shape
containing less than 20% Cr and those containing more than curve. At temperatures below 600°C (1110°F), corrosion is
20% Cr. Alloy modifications based on the 18Cr-8Ni steels, believed to be low because the trisulfate exists in solid form.
such as TP304H, 316H, 347H, and Tempaloy A-1, and alloys Above 750°C (1380°F), corrosion rates are once again low, as
with lower chromium and higher nickel contents, such as 17-14 the trisulfates vaporize. The worst corrosion problem is in the
CuMo steel, Esshete 1250, and Tempaloy A2, fall into the range 600 to 750°C (1110 to 1380°F). The data indicate that
classification of steels with less than 20% Cr. The allowable the high-chromium alloys such as type 310 stainless steel and
tensile stresses for steels in this class are compared in Figure 8. Incoloy 800H are superior to the other alloys tested, and that
Tempaloy A1, Esshete 1250, and 17-14 CuMo steel are found to Inconel 671 (Ni-50Cr) or its matching weld metal IN72 is
offer major improvements over the 300 series stainless steels. It virtually immune to attack. Lower-chromium stainless steels,
has been reported that grain-size modifications of AISI type such as type 316H, type 321H, and Esshete 1250, show
347H stainless steel can in some instances lead to rupture considerable susceptibility to attack. The alloy most susceptible
properties somewhat better than those of Tempaloy A-1(16). to attack seems to be the 17-14 CuMo alloy used in the
Several high-creep-strength alloys containing more than Eddystone 1 plant. Results of field probe studies confirm the
20% Cr, such as NF707, NF709, and HR3C, have been following ranking of alloys in increasing order of corrosion
developed, and offer low-cost alternatives to Incoloy 800 for resistance: T91, HCM12, type 347 stainless steel, Incoloy 800,
use in the temperature range from 650 to 700°C (1200 to and Inconel 671(21). In addition to alloy selection, other “fixes’
1290°F). A comparison of the ASME Code allowable stresses to minimize fire-side corrosion, such as shielding of the tubes
for the high-chromium alloys is shown in Figure 9. Clearly, may also be applied, if economical(22).
NF709 and HR3C are leading candidates for use in the highest- Results of extensive field tests have also been reported by
temperature applications. The latter steel was approved for use Blough(23). This was based on a collaborative study by EPRI,
in boilers by ASME as SS310NbN. The highest creep strength IHI and F-W who carried out extensive laboratory and field
is achieved in Inconel 617, which contains 22% Cr, but it is also tests in 3 boilers, two of them fueled with somewhat corrosive
likely to be the most expensive alloy to use, due to its high Ni Eastern bituminous US coal, one fueled with a supposedly non-
content. corrosive Western low sulfur subbituminous coal. The
A comparison of allowable temperatures at a constant experiments were carried out using air cooled, retractable
allowable stress of 49 MPa (7 ksi), as a function of chromium probes, inserted in finishing superheater or reheater areas.
content, is shown in Figure 10. With increasing chromium, a Metal temperatures were maintained in the 600-690°C range
discontinuity is seen in the allowable metal temperatures of (1250-1300°F). Exposure time was 16,000 hrs with samples
austenitic steels, rising about 50°C (90°F) above those of removed after 4000, 12,000 and 16,000 hrs. Figure 14 shows
ferritic steels(17). In terms of increasing temperature capability, metal losses observed in one of the boilers, using an Eastern
stable austenitic alloys offer the highest capability, followed by bituminous coal, Figure 15 those observed in the boiler using
metastable austenitic steels, and then by ferritic steels. The subbituminous Western coal. The losses observed were about
fully enhanced, stable austenitic alloys are clearly capable of the same but the corrosion mechanisms were different. Tubes
operating under phase 2 steam conditions (650°C, or 1200°F). from the boilers using eastern bituminous coals showed the
classic liquid ash corrosion in the 10 and 2 o’clock positions of
2.3.2 Fire-side Corrosion the tube, where sulfur rich fly ash impacts on the tube.
Fireside corrosion results from the presence of molten Potassium rich sulfate was found in the ash deposits, and metal
sodium-potassium-iron trisulfates. Because resistance to fire- wastage was caused by internal oxidation and sulfidation,
side corrosion increases with chromium content, the 9 to 12% because a fully protective Cr2O3 scale could not form in the
Cr ferritic steels are more resistant than the 2-1/4Cr-1Mo steels presence of sulfur rich deposits. With increasing Cr content in
currently used. The 12% Cr steel in turn shows better corrosion the alloy the Cr2O3 scale became more protective, but in all
resistance than 2-1/4% Cr steel and 9% Cr steel, as shown in alloys internal oxidation and sulfidation occurred in Cr depleted
Figure 11(18). Stainless steels and other superalloys containing zones below the scale.
up to 30% Cr represent a further improvement. Increasing the The corrosion morphology of the tubes from the boiler
chromium content beyond 30% results in a saturation effect on using Western subbituminous coal was similar, but the area of
the corrosion resistance at least in the laboratory, as shown in major attack was on the side of the tube facing away from the
Figure 12(19). For practical purposes, when corrosive conditions

6 Copyright © 2000 by ASME

flue gas stream, where deposits rich in very fine CaSO4 were HCM9M and comparable to that of fine-grained 347H for
found. exposure to the high-temperature region of the reheater.
From the results presented above, it may be concluded that Subsequent monitoring over a period of three years has borne
substantial superheater corrosion can occur, especially in high out their earlier conclusions(27). In addition to the inherent
strength austenitic alloys with a low chromium content. For resistance of HCM12M steel to steam-side oxidation,
most coals, high strength modified Alloy 800 type alloys such Masuyama et al suggest that the tendency toward exfoliation of
as NF709, will probably have sufficient corrosion resistance, oxide scale would also be less for this alloy than for austenitic
while for more corrosive coals modified SS 310 type alloys, e.g. steels(26,27). Additional improvements in 9 to 12% Cr steels may
HR3C, should given an extra margin of safety. It is of interest be possible by extending the chromizing(28,29) and chromate
to note here that the T-91 sample exposed in the low sulfur coal conversion treatments(30) that currently are applied to lower-
fueled boiler had a corrosion loss similar to SS 347, which is alloy steels, grain refinement during heat treatment has been
considerably less than that of SS 304 and 17-14CuMo. A shown to be clearly beneficial as well. Internal shot blasting is
probable reason is that scales and deposits usually adhere tight also known to improve the steam oxidation resistance of 300
to ferritic/martensitic steels, but spall readily from all austenitic series stainless steels by enhancing chromium diffusion. It is
steels. therefore anticipated that these steels would be used in the fine-
Based on the favorable results from the air-cooled probes grain and shot-peened conditions. Results of steam oxidation
in one of the plants, the SS304M reheater, which suffered from tests at 650°C (1200°F) for times up to 2000 h have been
severe alkali sulfate corrosion was replaced by one made from reported for several austenitic steels(31).
SS310 NbN (HR3C).(24) Test sections of other alloys were built
into the reheater and carefully monitored. It was found that 2.3.4 Summary of SH/RH Tube-Material Status
310NbN (HR3C) was a satisfactory material for 90% of the Based on the discussion so far recommendations for
reheater, with less than 0.25 mm/yr (10 mils/yr) corrosion. materials selection have been made in Table 5. For phase 0
However in one area, about 10 tubes wide and 10 ft (3m) high, steam conditions, alloys T91, HCM12M, and AISI type 304
corrosion rates ranged from 0.5 – 1.25 mm/yr (20-50 mils/yr). stainless steel are viable candidates for superheater and reheater
Here the corrosion resistance of SS310 was about the same as tubing, provided that fire-side corrosion is not a major problem.
that of SS347 and alloy 800H. Only a Cr-Ni steel (Cr30A) with Under mildly corrosive conditions, 310NbN stainless steel may
30% Cr had significantly lower corrosion rates, ranging from be the most cost-effective option. For severe corrosion
0.125 – 0.5 mm/yr (5 – 20 mils/yr). It is concluded that cladding, SS304 with IN72 (44%Cr) is recommended.
increasing the Cr content of the alloy from 18-20% to 23-25% For intermediate-temperature applications corresponding to
will only significantly increase corrosion resistance, when the phase 1 steam conditions (595°C, or 1100°F), Tempaloy A-1
corrosivity of the deposits is moderate, i.e. ≤ 0.5 mm/yr (20 and type 347 fine-grained stainless steel are deemed to be
mils/yr for 18-8 stainless steels). For more corrosive adequate in the absence of corrosive conditions. Under mildly
conditions, co-extruded tubes or weld overlay claddings corrosive conditions, 310NbN stainless steel may offer the best
containing at least 40% Cr are strongly recommended. combinations of creep strength and corrosion resistance. For
severe corrosion, cladding with IN72 is recommended.
2.3.3 Steam-side oxidation For phase 1B i.e. 620°C conditions Super 304H, Tempaloy
Steam-side oxidation of tubes and exfoliation of the oxide AA1, Esshete 1250 and 17-14 CuMo may be acceptable under
scale and its consequence in terms of solid-particle erosion non-corrosive conditions. For mildly corrosive conditions
damage to the turbine are well known. This problem is alloys with 20-25% Cr such as HR3C, and NF709 will have the
expected to be more severe in advanced steam plants, because best combination of creep strength and corrosion resistance.
the much higher steam temperatures employed are likely to For severe corrosion, cladding with IN72 is again
cause more rapid formation of oxide scale. recommended.
Very limited data are available regarding the steam-side For the highest-temperature application corresponding to
scale-growth characteristics of the ferritic tubing alloys. In a phase 2 steam conditions (650/650°C, or 1200/1200°F), the
study by Sumitomo Metal Industries(25), the oxide growth in creep strength requirements are met by Inconel 617, 17-14
steam for alloys T22 (2-1/4Cr-1Mo), T9, HCM9M, and the CuMo steel, Esshete 1250 and NF709. Among these alloys, 17-
modified 9Cr-1Mo (T91) were compared based on 500 hr tests. 14 CuMo steel and Esshete 1250 have inadequate corrosion
Results showed the superiority of the T91 alloy over the other resistance and will have to be clad with corrosion-resistant
alloys. Masuyama et al compared alloys HCM12, HCM9M, claddings of Inconel 671 if corrosive conditions are present.
321H, and 347H in field tests in the temperature range 550 to NF709 and CR30A may be used without any corrosion
625°C (1020 to 1155°F) over a period of one year(26). Samples protection for mildly corrosive conditions, but will require
were inserted in the tertiary and secondary superheaters and cladding with IN72 for severely corrosive conditions..
reheaters. From the results, they concluded that the resistance
to steam oxidation of HCM12 is superior to those of 321H and

7 Copyright © 2000 by ASME

2.4 Choice of Materials for Waterwalls more than 20% Cr are needed to assure acceptably low
corrosion rates.
2.4.1 Metal Temperature Concerns
This issue has been discussed recently by Blum(32). In 3.0 SUMMARY AND CONCLUSIONS
boilers operating at 625°C/32 MPa, maximum midwall Literature pertaining to materials technology for boilers in
temperatures can be as high as 500-525°C, depending on ultra supercritical pulverised coal power plants has ben
magnetite deposits at the inside of the tube. This means that the reviewed. Extensive development in strengthening of 9 to 12%
creep resistance of standard low alloy ferritic steels such as T-11 ferritic steels have resulted in temperature/pressure capabilities
is not adequate. Originally T-91 steel was the only suitable well over the conventional framework of 538°C/17 MPa
substitute. Under the COST program(33) it was demonstrated (1000°F/2400 psi) for the steam. Nearly two dozen plants have
that this material can be fabricated into waterwalls. However a been commissioned worldwide with main steam temperatures of
postweld heat treatment is required, which is difficult to do in 585 to 600°C (1080-1112°F) and pressures of 24 to 30 MPa
the field. Two steels containing 2.5 and 12Cr% respectively (3400-4200 psi). Specific materials developments with respect
developed by Sumitomo and MHI are more promising in that to key components are as follows:
they do not require preheat or postweld heat treatment.(32,34) For heavy section components such as pipes and headers,
Both steels have creep strength in the same range as T-91 and minimising thermal fatigue has been a major driver in addition
use similar precipitation strengthening mechanisms. Especially to achieving high creep strength. For this reason, alloy
the 2.5%Cr steel appears promising for this application. It also development has focussed on ferritic steels containing 9-12%
has recently been approved by the ASME boiler code Cr. Optimisation of C, Nb, Mo and V and partial substitution of
committee as T-23. Test panels are now in service in various W for Nb in the 9-12% Cr ferrtitic steels has resulted in three
boilers. new alloys HCM12A, NF616 and E911 (P92, P122 and E911)
capable of operating up to 620°C (1150°F) at steam pressures
2.4.2 Waterwall Corrosion Concerns up to 34 MPa (4800 psi). Beyond 620°C oxidation resistance
Recent reductions in NOx emissions, mandated by the may become an additional limiting factor, especially for the 9%
Environmental Protection Agency in the USA have led to the containing steels. A newer class of 12% Cr alloys NF12 and
introduction of deeply staged combustion systems, in which the SAVE12, containing cobalt and additional W is being evaluated
air/fuel ratio is significantly less than 1, and additional for possible 650°C (1200°F) application. It appears from
combustion air is added above the burners via overfire air ports. preliminary results that austenitic steels or Nickel alloys would
Several boilers in the USA retrofitted with such systems have be needed for temperatures exceeding 650°C.
reported severe corrosion of low alloy steel waterwalls, with For SH/RH tubes steamside oxidation resistance, and
metal losses in the 1-3 mm/yr (40-120 mil/yr) range. fireside corrosion resistance are major drivers in addition to
Supercritical units are generally more severely affected than creep resistance. Furthermore, tube metal temperatures often
subcritical units and severe corrosion is generally limited to exceed the steam temperature by as much as 28°C (50°F) It is
coals with more than 1%S. However above 1%S there is no unlikely that any of ferritic steels can be used in the finishing
strict correlation between S and corrosion rate. The highest stages of SH/RH circuits at steam temperatures exceeding
corrosion losses are found in regions where H2S rich 565°C (1050°F). Austenitic steels need to be used at these
substiochiometric flue gas mixes with air from the overfire air higher temperatures. Depending on the corrosivity of the coal
ports. Laboratory studies indicate that the high corrosion rates used, higher Cr steels or clad steels may be required. For
cannot be explained by the presence of H2S and CO in the flue 620°C application, Super 304H, Tempalloy AA1, Esheat 1250
gas alone. Work by Kung(35) has shown that corrosion rates in and 17 CW-MO are acceptable under non corrosive conditions
gas mixtures, actually found in boilers, containing 500-1500 pm while 20-25% Cr alloys such as HR3C, NF709 and cladding
H2S and 5-10% CO, are generally less than 0.5 mm/yr (20 with IN72 are recommended for more corrosive conditions.
mils/yr) at 450°C. More recently it was shown that the presence Several candidate alloys Inconel 617, NF709 and Cr30A and
of FeS deposits can greatly increase the corrosion rate, but only alloys clad with Inconel 671 (50% Cr) are available for use at
under alternating oxidizing/reducing conditions or oxidizing 650°C.
conditions alone. Figure 16 shows corrosion losses of a low For upper waterwall sections, two new steels containing 2.5
alloy steel, T-91 and SS-304 in the presence of FeS containing and 12% Cr known as HCM2(T23) and HCM 12 respectively
deposits and a gas mixture containing 1% oxygen. Although the are very promising in terms of creep strength and weldability.
corrosion rates are probably artificially high, because of the They are suitable for use in the range of 595-650°C steam
short duration of the test, it is clearly demonstrated that low conditions purely from a creep strength point of view. When
alloy steels will corrode quite rapidly in the presence of FeS fireside corrosion in low NOx boilers is an issue, these alloys
deposits and an oxidizing gas. The tests further show that will have to be clad or weld overlaid with alloys containing
claddings or weld overlays containing at least 18 and preferably more than 18-20% Cr.

8 Copyright © 2000 by ASME

4.0 REFERENCES Generation, R. Viswanathan and J.W. Nutting, Ed.; IOM
1. K.H. Mayer et al, “New Materials for Improving the Communications Ltd., London, pp 133-142, 1999.
Efficiency of Fossil-fired Thermal Power Stations”, 16. K. Yoshikawa et al, Therm. Nucl. Power, Vol. 12 (No.
International Joint Power Generation Conference, PWR-Vol. 12), 1985, p 1325-1339.
33, ASME, 1998, pp 831-841. 17. F. Masuyama, H. Haneda and B.W. Roberts, “Update
2. R.D. Hottenstine, N.A. Phillips and R.A. Dill, Survey and Evaluation of Materials for Improved Coal-Fired
“Development Plans for Advanced Fossil Fuel Power Plants”, Power Plants”, Report CS-5181-SR, EPRI, Palo Alto, 1988, pp
Report CS-4029, EPRI, Palo Alto, 1985. 5.85 to 5.108.
3. M. Gold and R.I. Jaffee, “Materials for Advanced 18. H. Teranishi et al, presented at the International
Steam Cycles”, ASM J. of Materials for Energy Systems, Vol. 6 Conference on High Temperature Alloys, Preprint Paper No.
(No. 2), 1984, p 130-145. 21, Petten, The Netherlands, Oct 15-17, 1985.
4. D.V. Thornton and K.H. Meyer, “European High 19. T. Ikeshima, Bull. Japan Inst. Metals, Vol. 22 (No. 5),
Temperature Materials Development” in Advanced Heat 1983, p 389.
Resistant Steels for Power Generation, R. Viswanathan and J.W. 20. Ohtomo et al, High Temperature Corrosion
Nutting, Ed.; IOM Communications Ltd., London, pp 349-365, Characteristics of Superheater Tubes, Ishikawajima Harima
1999. Industries, Engg. Rev., Vol. 16 (No. 4), Oct 1983.
5. R. Viswanathan and W.T. Bakker, Materials for Ultra 21. A.L. Plumley and W.R. Roczniac, Coal Ash Corrosion
Supercritical Fossil Power Plants, Report TR-114750, EPRI, Field Testing of Advanced Boiler Tube Materials, in
Palo Alto, January 2000. Proceedings of the Second International Conference on
6. W.T. Bakker, “Materials for Advanced Boilers”, in Improved Coal-Fired Power Plants, Electric Power Research
Advanced Heat Resistant Steels for Power Generation, R. Institute, Palo Alto, CA, Nov 1-4, 1988.
Viswanathan and J.W. Nutting, Ed.; IOM Communications Ltd., 22. A.F. Armor, R.I. Jaffee and R.D. Hottenstine,
London, pp 435-455, 1999. “Advanced Supercritical Power Plants – The EPRI
7. F. Masuyama, “New Developments in Steels for Power Development program, Proc. of American Power Conference,
Generation Boilers”,in Advanced Heat Resistant Steels for Vol. 46, 1984, p 70.
Power Generation, R. Viswanathan and J.W. Nutting, Ed.; IOM 23. J.L. Blough et al, “Superheater Corrosion – Field Test
Communications Ltd., London, pp 33-48, 1999. Results”, Report TR-103438, EPRI, Palo Alto, Nov 1993.
8. W. Garrison and R.F. Buck, “An Overview of the 24. J.L. Blough et al, “superheater Corrosion in Ultra
Development of Advanced 9-12% Cr Steels,” In ASM Supercritical Power Plants, Long-Term Field Exposure at TVA’s
Symposium on Materials for Rotating Machinery, Oct 1999, Gallatin Plant”, EPRI Report TR-111239, EPRI, Palo Alto,
Cincinnati. 1999.
9. R. Viswanathan, “Damage Mechanisms and Life 25. “Properties of Super 9Cr Steel Tube (ASTM) A 213-T
Assessment of High-Temperature Components”, ASM 91,” Report 803 F-No. 1023, Sumitomo Metal Industries, July
International, Metals Park, OH, 1989. 1983.
10. H. Haneda et al, In Proceedings of the Third 26. F. Masuyama, H. Haneda, T. Daikoku, and T.
International Conference on Steel Rolling, Tokyo, September 2- Tsuchiya, “Development and Applications of a High Strength,
6, 1985, pp 669-676. 12% Cr Steel Tubing with Improved Weldability”, Technical
11. T. Topoda et al, “Development of Thick Walled Pipes Review, Mitsubishi Heavy Industries, Ltd., Japan, Oct. 1986, p
and Headers of Modified 9Cr Steel”, Proc. of the Second 229-237.
International Conference on Improved Coal-fired Power Plants, 27. F. Masuyama, H. Haneda, K. Yoshikawa, and A. Iseda,
2-7 Nov. 1988, Palo Alto, CA, EPRI Report GS-6422, pp 36-1. Three Years of Experience with a New 12% Cr Steel in
12. B.W. Roberts et al, “Thick Section Welding of Superheater, in Advanced in Materials Technology for Fossil
Modified 9Cr-1Mo (P91) Steel”, EPRI Report TR-101394, Fuel Power Plants, R. Viswanathan and R.I. Jaffee, Ed.,
September 1992. American Society for Metals, Metals Park, OH, 1987, p 259-
13. T. Fujita et al, “Development of a 9Cr Steel” in EPRI 266.
Report CS-5581-SR, p 5-201. 28. A.J. Blazewicz and M. Gold, “Chromizing and
14. E. Metcalfe, Ed., Proc. “New Steels for Advanced Turbine Solid Particle Erosion”, ASME Paper No. 78, JPGC
Power Plants”, EPRI Report TR-104952, 1995. PWR-7, Joint ASME/IEEE/ASCE Power Generation
15. F. Masuyama and F.T. Yokoyama, NF616 Fabrication Conference, Dallas, September 1978.
Trials in Comparison with HCM12A, EPRI Report TR-104952, 29. P.L. Daniel et al, “Steamside Oxidation Resistance of
p 30, 1995. Chromized Superheater Tubes”, CORROSION 80, NACE
15b. W. Bendik et al, “New 9-12% Cr Steels for Boiler Conference, Chicago, May 1980.
Tubes and Pipes: Operating Experiences and Future 30. J.M. Rehn et al, “Controlling Steamside Exfoliation in
Developments”, in Advanced Heat Resistant Steels for Power Utility Boiler Superheaters and Reheaters”, Paper No. 192,
CORROSION 80, NACE Conference, Chicago, May 1980.

9 Copyright © 2000 by ASME

 31. K. Kubo, S. Murase, M. Tamura, and T. Kanero, Liege, Belgium, Kluwer Ac. Publ. Dordrecht, The Netherlands,
Application of Boiler Tubing Tempalloy Series to the Heat 15.
Exchanger of Advanced Coal-Fired Boilers, in Proceedings of 33. C.J. Franklin and C. Henry, “Materials Development
the First International Conference on Improved Coal-Fired and Requirements for Advanced Boilers”, Reference 31, 89.
Power Plants, A.F. Armor, W.T. Bakker, R.I. Jaffee, and G. 34. F. Masuyama, Y. Sawaragi et al, “Development of a
Touchton, Ed., Report CS-5581-SR, Electric Power Research Tungsten Strengthened Low Alloy Steel with Improved
Institute, Palo Alto, CA, 1988, p 5-237 to 5-254. Weldability”, Reference 31, 173.
32. R. Blum, “Materials Development for Power Plants 35. S.K. Kung, “Prediction of Corrosion Rate for Alloys
with Advanced Steam Parameters. Utility Point of View”, Proc. Exposed to Reducing/Sulfidizing Combustion Gases”,
Materials for Advanced Power Eng., 1991, 3-6 Oct. 1994, Corrosion 97, NACE 1997, 97-136.

Table 1
Steam conditions for coal-fired plants in EPRI program(2)

EPRI Pressure Temperature

Program
Phase MPa psig °C °F

0 31.0 4500 566/566/566 1050/1050/1050

1 31.0 4500 593/593/593 1100/1100/1100
1B 31.0 4200 620/620/620 1150/1150/1150
2 34.5 5000 649/649/649 1200/1200/1200

Table 2
Evolution of Four Generations of Ferritic Steels (Based on Reference 7)
Generation Years Alloy Modifications Strength 105 hr Creep Rupture Example Alloys Maximum Metal Use
Achieved MPa Temp. °C
1 1960-70 Addition of Mo or 60 EM12, HCM9M, 565
Nb, V to simple 12Cr HT9, Tempaloy
and 9Cr Mo steels F9, HT91
2 1970-85 Optimization of C, 100 HCM12, T91, 593
Nb, V HCM2S
3 1985-95 Partial substitution of 140 P-92, P-122 620
W for Mo (HCM12A,
NF616)
4 Emerging Increase of W and 180 NF12, SAVE12 650
addition of Co

10 Copyright © 2000 by ASME

 Table 3
Nominal Chemical Compositions of Ferritic Steels for Boilers
Specification Chemical Composition (mass%) Manu-
facturers
Steels ASME JIS C Si Mn Cr Mo W Co V Nb B N Others
1-1/4 T11 T11 0.15 0.5 0.45 1.25 0.5 -- -- -- -- -- -- --
Cr
NFIH 0.12 -- -- 1.25 1.0 -- -- 0.20 0.07 -- -- -- Nippon Steel

2Cr T22 T22 STBA24 0.12 0.3 0.45 2.25 1.0 -- -- -- -- -- -- --

HCM2S T23 STBA24J1 0.06 0.2 0.45 2.25 0.1 1.6 -- 0.25 0.05 0.003 -- -- Sumitomo

Tempaloy 2.0 0.6 1.0 0.25 0.05 -- -- NKK

F-2W
9Cr T9 T9 STBA26 0.12 0.6 0.45 9.0 1.0 -- -- -- -- -- -- -- Vallourec-
Mannesman
HCM9M -- STBA27 0.07 0.3 0.45 9.0 2.0 -- -- -- -- -- -- -- Sumitomo

T91 T91 STBA28 0.10 0.4 0.45 9.0 1.0 -- -- 0.20 0.08 -- 0.05 0.8Ni Vallourec-
Mannesman
Sumitomo
E911 0.12 0.2 0.51 9.0 0.94 0.9 -- 0.20 0.06 0.06 0.25Ni
12Cr HT91 (DIN x20CrMoV121) 0.20 0.4 0.60 12.0 1.0 -- -- 0.25 -- -- -- 0.5Ni Vallourec
Mannesman
HT9 (DIN 0.20 0.4 0.60 12.0 1.0 0.5 -- 0.25 -- -- -- 0.5Ni Vallourec
x20CrMoWV121) Mannesman
Tempaloy 12.0 0.7 0.7 -- NKK
F12M
HCM12 SUS410J2T 0.10 0.3 0.55 12.0 1.0 1.0 -- 0.25 0.05 0.03 --
B
TB12 -- -- 0.08 0.05 0.50 12.0 0.50 1.8 -- 0.20 0.05 0.30 0.05 0.1Ni
HCM12A T122 SUS410J3T 0.11 0.1 0.60 12.0 0.4 2.0 -- 0.20 0.05 0.003 0.06 1.0Cu Sumitomo
B
NF12 -- -- 0.08 0.2 0.50 11.0 0.2 2.6 2.5 0.20 0.07 0.004 0.05 -- Nippon Steel
SAVE12 -- -- 0.10 0.3 0.20 11.0 -- 3.0 3.0 0.20 0.07 -- 0.04 0.07Ta, Sumitomo
0.04Nd

11 Copyright © 2000 by ASME

 Table 4
Nominal Chemical Compositions of Austenitic Steels for Boiler (wt%)
Specifications
ASME JIS C Si Mn Ni Cr Mo W V Nb Ti B Others
18Cr-8Ni TP304H SUS304HTB 0.08 0.6 1.6 8.0 18.0 -- -- -- -- -- -- --

Super 304H SUS304J1HT 0.10 0.2 0.8 9.0 18.0 -- -- -- 0.40 -- -- 3.0Cu, 0.10N
B
TP321H SUS321HTB 0.08 0.6 1.6 10.0 18.0 -- -- -- -- 0.5 -- --
Tempaloy A- SUS321J1HT 0.12 0.6 1.6 10.0 18.0 -- -- -- 0.10 0.08 -- --
1 B
TP316H SUS316HTB 0.08 0.6 1.6 12.0 16.0 2.5 -- -- -- -- -- --
TP347H SUSTP347H 0.08 0.6 1.6 10.0 18.0 -- -- -- 0.8 -- -- --
TB
TP347 HFG 0.08 0.6 1.6 10.0 18.0 -- -- -- 0.8 -- -- --
15Cr-15Ni 17-14CuMo 0.12 0.5 0.7 14.0 16.0 2.0 -- -- 0.4 0.3 0.006 3.0Cu
Esshete 0.12 0.5 6.0 10.0 15.0 1.0 0.2 1.0 -- 0.06 --
1250
Tempaloy A- 0.12 0.6 1.6 14.0 18.0 1.6 -- -- 0.24 0.10 --
2
20-25Cr TP310 SUS310TB 0.08 0.6 1.6 20.0 25.0 -- -- -- -- -- --
TP310NbN SUS310J1TB 0.06 0.4 1.2 20.0 25.0 -- -- -- 0.45 -- -- 0.2N
NF707* 0.08 0.5 1.0 35.0 21.0 1.5 -- -- 0.2 0.1 -- --
Alloy 800H NCF800HTB 0.08 0.5 1.2 32.0 21.0 -- -- -- -- 0.5 -- 0.4Al
Tempaloy A- SUS309J4HT 0.05 0.4 1.5 15.0 22.0 -- -- -- 0.7 -- 0.002 0.15N
3* B
NF709* SUS310J2TB 0.15 0.5 1.0 25.0 20.0 1.5 -- -- 0.2 0.1 --
SAVE25* 0.10 0.1 1.0 18.0 23.0 -- 1.5 -- 0.45 -- -- 3.0Cu, 0.2N
HighCr-High CR30A* 0.06 0.3 0.2 50.0 30.0 2.0 -- -- -- 0.2 -- 0.03Zr
Ni
HR6W* 0.08 0.4 1.2 43.0 23.0 -- 6.0 -- 0.18 0.08 0.003
Inconel 617 0.40 0.4 54.0 22.0 8.5 -- -- -- -- -- 12.5Co, 1.2Al
Inconel 0.05 -- -- 51.5 48.0 -- -- -- -- -- -- --
671**

* Not ASME code approved.

** Low strength material for use in co-extruded tubing. For weld overlays, IN72 (44%Cr-bal Ni) is the matching weld wire

12 Copyright © 2000 by ASME

Table 5
Candidate Materials for Advanced Supercritical Plants for Various Steam Conditions
Phase 0 Phase 1 Phase 1B Phase 2
Component 31MPa (4500 psi) 31MPa (4500 psi) 31MPa (4500 psi) 34.5MPa (5000 psi)
565/565/565°C 593/593/593°C 620/620/620°C 650/650/650°C
(1050/1050/1050°F) (1100/1100/1100°F) (1150/1150/1150°F) (1200/1200/1200°F)
Headers/steam P22, HCM2S (P23) P91, P92, P122, P92, P122 SAVE12+
pipes P91, P92, P122 E911 E911, NF12, NF12+
SAVE12
Finishing SH non- T91, 304H, 347 TP347 HFG NF 709 NF 709
corrosive Super 304 H/P-122* Super 304 H Inconel 617
Corrosive 310 NbN (HR3C) 310 NbN (HR3C) 310 NbN (HR3C) Cr 30A
SS347/IN72** Super 304H/IN72** NF 709/IN72**
Finishing RH Same as SH Same as SH Same as SH Same as SH
Water wall
Lower wall C steel T11, T12, T22 Same as Phase 1
Upper wall T11, T12, T22 T23 (HCM12) Same as Phase 1

For low NOx Clad with alloy

Boilers + High S containing >20% Cr
coal or chromized Same as Phase 0 Same as Phase 0 Same as Phase 0
* High strength ferritic alloys with 9%Cr are suitable for steam piping and headers, but may suffer excessive fire side oxidation. 12Cr
steels may be suitable, but further testing is needed.
** IN72 (44Cr, bal Ni) weld overlay for corrosion protection
+
Developmental Alloy

Table 6
Application of New Tungsten-Bearing Steels in European Power Stations (Ref. 15b)

Power Station Material Grade Size Component Steam Installation

Conditions°C/MP
a
Vestkraft Unit 3 P92 (NF616) ID 240 x 39 Straight PipeMain 560/25 1992
Steam
Nordjyllands- P92 (NF616) ID 160 x 45 Header 582/29 1996
vaerket P122 (HCM12A)
Schkopau Unit B E911 ID 550 x 24 Induct. BendHot 560/7 1996
Reheat
StaudingerUnit 1 E911 ID 201 x 22 Induct. BendMain 540/21.3 1996
Steam
SkaerbaekUnit 3 E911 ID 230 x 60 Induct. BendMain 582/29 1996
Steam
GK Kiel P92 ID 480 x 28 Header 545/5.3 1997
VEW E911 OD 31.8 x 4 Superheater 650
1998
Westfalen E911 ID 159 x 27 Steam Loop 650/18 1998
Westfalen P92 ID 159 x 27 Steam Loop 650/18 1998

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Figure 1
Improvements in heat rate (efficiency) achieved by increasing steam temperature and pressure using single and double reheat
cycles (Ref. 1), compared to the base case of 535°C/18.5 MPa

Figure 2
Historic evolution of materials in terms of increasing creep rupture strength(7)

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Figure 3
Evolution of ferritic steels for boilers(7)

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Figure 4
Evaluation of authentic steels for boiler(7)

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Figure 5
Comparison of allowable stresses of ferritic steels for boiler (Based on Reference 7)

Figure 6
Comparison of allowable stresses and sectional view of main steam pipes designed at 570°C and 600°C (15)

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Figure 7
Cost of P-22, P-91 and P-122 steels header materials as a function of temperature at 31 MPa steam pressure(15)

Figure 8
Comparison of allowable stresses for 18Cr-8Ni and 15Cr steels (Ref. 17)

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Figure 9
Comparison of allowable stresses for austenitic alloys containing more than 20% Cr (based on Ref. 17)

Figure 10
Allowable metal temperatures at constant allowable stress of 49 MPa (7 ksi) as a function of chromium content for various
alloys (Ref. 17)

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Figure 11
Relationship between hot-corrosion weight loss and temperature for ferritic steels(18)

Figure 12
Relationship between hot-corrosion weight loss and chromium content for various alloys(19)

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Figure 13
Comparison of fire-side corrosion resistance of various alloys(20)

Figure 14
Metal losses of various superheater steels in a boiler using bituminous eastern U.S. coals(23)

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Figure 15
Metal losses of various superheater steels in a boiler subbituminous western U.S. coals(23)

Figure 16
Corrosion of steels containing 0.5-18% Cr under FeS containing deposits in oxidizing flue gas

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