Current Limitations of High-Temperature Alloys in Practical Applications

Oxidation of Metals, Vol. 44, Nos.
1/2, 1995
Current Limitations of High-Temperature Alloys

in Practical Applications
John Stringer* and Ian G. Wrightt:~
Received March 24, 1995
There are several engineering systems which require materials of construction

to tolerate elevated temperatures, and aggressive environments of one kind or
another; and where, furthermore, the performance of the system is limited by
the materials capability. This paper reviews a number of these systems, drawn
principally from the electric power industry, and describes both the current
approaches to improving the materials capability, and potential directions for
research and development for the future. Particular emphasis is given to cases
where the problems related to oxidation and high-temperature corrosion are
of major importance.
KEY WORDS: oxidation; corrosion; high temperatures; erosion; wear.
INTRODUCTION
There are a number of engineering systems within which there are regions
of high temperature. These include, for example, metals extraction systems
such as blast furnaces; materials treatment systems such as steel heat treat-
ment furnaces or pottery kilns; heat engines such as gas turbines, and high-
temperature electrochemical systems such as molten carbonate fuel cells.
The chemical environment can also vary widely, from simple oxidizing
environments such as air or clean combustion gases with excess air, through
mixed oxidant environments, such as clean substoichiometric combustion
*Electric Power Research Institute, Palo Alto, California.

tCorrosion Science and Technology, Metals and Ceramics Division, Oak Ridge National
Laboratory, Oak Ridge,Tennessee.
~At the time of the preparation of this paper, Dr. Wright was a Visiting Scientist at the Electric
Power Research Institute, on leave from Battelle Columbus Laboratories, Columbus, Ohio.
265
0030-770X/95/0800~0265507.50/0 9 1995PlenumPublishingCorporation
266 Stringer and Wright
gases, or combustion gases containing sulfur, to carburizing atmospheres

such as those in reformers, or sulfidizing atmospheres such as those in sulfur
boilers. The high-temperature environment may be gaseous, as in those
examples quoted in the last sentence, liquid, as in molten carbonate fuel
cells or glass melters, or solid, as in solid oxide fuel cells. In addition to the
potentially aggressive chemical environment, the high-temperature compo-
nent may be subjected to mechanically aggressive factors, such as high-
velocity particle-containing gas streams, as for example in the combustion
gas in a pressurized fluidized bed entering the expansion turbine, or the
fly-ash laden gas in a conventional pulverized-coal-burning boiler passing
through the heat-exchanger tube banks; or low-velocity high-particle-density
environments, such as those in the bed of fluidized-bed combustors.
In most of these systems, the high-temperature region is of crucial
importance to the overall process, and the materials of construction for
this region present significant problems, both in terms of the maximum
temperature that can be attained, the maximum size of the hot region, and
the lifetime of this part of the system. The critical properties required of
the materials of construction may include strength, toughness, repairability,
thermal conductivity, chemical stability, and coefficient of thermal expan-
sion, among others; and it is important to recognize that the properties may
be critical not only at the maximum system temperature, but at intermediate
temperatures and even room temperature. A material selected for resistance
to the high-temperature environment may be sensitive to aqueous corrosion
or stress-corrosion cracking resulting from condensates during down times,
for example; or may have unacceptable low-temperature mechanical proper-
ties, such as very low toughness. A further requirement is that the material
must be stable, and not exhibit long-term aging processes which degrade
either the chemical or mechanical properties. This requirement is very impor-
tant, since by definition solid-state diffusion processes are relatively rapid at
high temperatures, so phenomena such as approach to equilibrium, grain-
boundary precipitation, grain-growth, recrystallization, and annealing, must
be considered. A well-known example is the tendency in high-alloy steels
and similar alloys to precipitate topologically close-packed (TCP) phases,
of which the best known is o--phase (sigma-phase).
In this paper, the majority of the examples given will be drawn from
the electric power industry, because this is the area of the authors' principal
experience; but it is important to recognize that related problems exist in
many other industries. Furthermore, most emphasis will be given to the
aspects of surface stability: mechanical stability in the cases of erosion,
abrasion, and wear; and chemical stability in the cases of oxidation and
high-temperature corrosion.
Current Limitationsof High-TemperatureAlloysin Practical Applications 267
The General Characteristics of the Problem

A designer has a number of alternatives for a system which contains a
high-temperature region. These include:
9 Cool the critical components. This may be done actively, by circulat-

ing a coolant through the component at risk, or passively, by lining
the structural member with a low-conductivity layer that separates it
from the hot zone.
9 Limit the temperature in the hot zone to a level that can be tolerated
by the available materials of construction. This usually carries ther-
modynamic penalties, but the costs of these must be balanced against
the costs of using higher-priced materials.
9 Moving the most critical components at risk to a lower-temperature
part of the system. This can sometimes be done in an initial design,
but is usually difficult to do as a remedial action if the problem
appears while the system is in service.
9 If the problem is related to the stability of the structural material in
the high-temperature environment, it may be possible to modify the
environment. This may mean altering the chemistry or (for example)
removing erosive particles.
9 In the case of surface stability, it may also be possible to use a coating
or other surface modification.
9 If these approaches do not work, or carry unacceptable economic
penalties, the designer may select an alternative material from the
standard well-understood materials available (replacing a low-alloy
steel by a higher-alloy steel, for example).
9 FinMly, if none of the preceding approaches are effective, it may be
necessary to develop a new structural material. In most cases,
designers wish to avoid this, because it takes a long time, not only
to develop the material, but to acquire sufficient engineering data, to
learn about the fabrication methods, and to learn about the main,
tainability aspects. However, this approach has been commonly used
in the development of gas turbines over the years.
In this paper, the following problems will be addressed:
9 Hot-section materials in gas turbines. This presents one of the most

severe situations for materials in terms of the strength and toughness
requirements coupled with the corrosive environment. The
approaches combine several elements:
Active cooling of the hot-section components

A passive cooling component, in the use of thermal barrier coatings

Coating for resistance to oxidation and corrosion
The development of new structural alloys
Materials for large coal-fired boilers. The approaches include
Identification of the root causes of tube failures
Selection of superheater tube materials for advanced steam conditions
Coextruded superheater tubes for boilers experiencing fireside corro-
sion
Coatings for water-wall tubes experiencing severe corrosion
Treatments to reduce steam-side oxide growth and exfoliation
Materials for gas-cooler heat exchangers in coal gasifiers. The
approaches include
Moderating the component temperature
Use of coatings and claddings
New materials
Other possibilities include
Modifying the environment chemistry
Modifying the cycle to enable the component to be moved to a loca-
tion where the conditions are less severe
Hot-Section Materials in Gas Turbines

The gas (or combustion) turbine uses the Brayton cycle. In this, air is
first compressed; then heated. The heated gas is then exhausted through an
expansion turbine: the turbine drives the compressor, and the excess energy
above that required for compression is available to do work. In a utility gas
turbine, the shaft drives the generator producing electricity. The gas leaving
the turbine is still quite hot, and the efficiency of the system can be improved
by making use of this heat in some way. The heating of the compressed air
may be direct or indirect. Essentially all utility gas turbines use direct heating,
in which fuel is mixed with the compressed air and burnt in a combustion
chamber. However, indirectly-fired turbine systems using fluidized bed com-
bustors or high temperature nuclear reactors as sources of heat have been
studied: the working fluid is a clean gas which is heated by means of a heat
exchanger. The indirectly-fired gas turbine may be open cycle, in which the
exhaust from the gas turbine is vented, or (more commonly) closed cycle, in
which the exhaust gas is returned to the low-pressure side of the compressor.
As with any heat engine, the efficiency is related to the difference
between the maximum and minimum (absolute) temperatures in the working
Current Limitationsof High-TemperatoreAlloysin Practical Applications 269
cycle, in this case the inlet temperature to the turbine and the exit tempera-
ture, divided by the maximum temperature. This is the Carnot efficiency and
real cycles achieve only a fraction of this. For example, in a modern gas
turbine the turbine inlet temperature may be 1288~ (2350~ and the
exhaust temperature may be 593~ (1100~ corresponding to a Carnot
efficiency of 44.5%; the actual efficiency of the engine is closer to 34%.
Improvements in efficiency can obviously be made by either increasing
the turbine inlet temperature or reducing the exhaust temperature at the
back end. The advantage of the gas turbine is that there is considerable
range to increase the inlet temperature, since the upper limit is the stoichio-
metric flame temperature: the practical limitations are in part set by the
available materials of construction and the effectiveness of the hot-section
materials cooling. Reduction of the exhaust temperature is much more
difficult in the simple cycle, and the best approach is to use the sensible heat
in the exhaust gas in some other way. In recent years, this has been done
by adding a steam cycle (Rankine cycle) by using the exhaust gas to boil
water in a heat-recovery boiler; the steam is then expanded through a steam
turbine in the usual way. The overall system is then referred to as a combined
cycle, and efficiencies as high as 58% have been attained.
The increases in the turbine inlet temperature in the early days of the
aviation gas turbine were paced by the capabilities of the alloys available for
the hot-section components. These components are, simply, the combustion
chamber; the duct that directs the hot gas from the combustion chamber
onto the turbine airfoils (this is called the transition piece in the case of a
can-type combustor design, and the inlet volute in the case of a silo-type
combustor design) ; and the first stages of the turbine itself. A stage consists
of a stationary airfoil followed by a rotating airfoil. The stationary airfoil
directs the gas flow onto the rotating stage and accelerates it, and in the
case of the first stage it is called the inlet nozzle guide vane.
Alloy Developments
The alloys that were developed for the nozzle and the rotor airfoils are
generally called superalloys, and may be either cobalt-based or nickel-based.
Historically, the progress of the development of these alloys is well-known:
a comprehensive description is contained in Sims, Stoloff and Hagel, 1 and
another by Gell et al.2; and a recent paper by Molloy3 summarizes the
development and current status of investment-cast superalloys. For both
classes of superalloys, the maximum temperature at which acceptable
strength could be retained leveled out at approximately 900~ (1652~
which is of the order of 65% of the absolute melting point of the pure metals.
As this limit was recognized, materials specialists started to examine the
possibility of using metals with higher melting points: the preferred candi-
dates were molybdenum and niobium. Alloys based on these materials did
not prove very successful, largely based on the poor oxidation resistance.
However, before this problem became crucial, the concept of cooling the
airfoils was developed, and a large part of the increase in the turbine inlet
temperature to the present levels is attributable to increasing sophistication
in cooling. This has carried with it a requirement for increasing sophistica-
tion in the casting of the airfoils, particularly the first-stage rotor blades, to
form the internal cooling passages.
Although cooling accounted for most of the increase in the turbine inlet
temperature over the last 20 years, there has also been some progress in the
capabilities of the alloys.4 A large part of this has addressed the issue of the
grain boundaries, since the sites of initial failure were grain boundaries
normal to the long axis of the airfoils. The initial progress was the addition
of small amounts of zirconium and boron to modify the grain boundaries.
The beneficial effects had been recognized for a long time: in 1957 Decker,
Rowe and Freeman 5 showed that 0.01% Zr+0.009% B added to Udimet
500 (the nominal compositions of the alloys mentioned in the text are listed
in Table I) could increase the creep rupture life [172 MPa, 870~ (25 ksi,
1600~ by a factor of 13, and elongation by a factor of 7. Other changes
in both composition and heat treatment have been aimed at modifying the
composition and distribution of carbides. However, again a radical change
has been made. This was the use of directional solidification to attempt to
produce a microstructure in which all the grain boundaries were parallel to
the long axis of the blade. There is some controversy about the originator
of this approach (see Ref. 4) but generally it is believed that VerSnyder6
and others at Pratt and Whitney Aircraft in the early 1960s were largely
responsible. Some changes in the composition of alloys was required, but
generally the directionally solidifed (DS) alloys are modifications of existing
superalloys. However, it was soon discovered that the addition of 2% Hf
coupled with directional solidification made it possible to use high-strength
eutectic compositions. DS alloys are widely used in both aircraft-derivative
engines, and in advanced industrial "Frame"-type engines; they would be
more widely used but for the need to optimize fabrication which leads to
greater costs.
The logical extension of this approach was to grow single-crystal (SC)
airfoils. Single crystal alloys offer futher flexibility in alloy design and associ-
ated increase in temperature capability for the following reasons7:
9 The directional solidification process results in large MC-type carbides

in some alloys, and these carbides are often precracked and initiate
matrix fatigue cracks under cyclic loading conditions.8'9
Current Limitations of High-Temperature Alloys in Practical Applications 271
.~o ~ ~
d 6 ~ r
0
0
r',
c',
0
C~
<
0
o
c.)
-~ z3
<
~ ~ ~ o~
<
A 1000
~. 800 CMSX-2/3, NASAIR 100
600
.= 400 40oc
~q / 140MPa
200
cc 100 DS MAR.M 247 \"~

" 80 SRR 99
0
r0 60
~ 40
700 750 800 850 900 9 0 10 0 1050 1100
Temperature (~
Fig. 1. 10,000 h rupture strength of the single-crystal super-
alloys CM SX-2 and -3, Nasair 100 and SRR 99 compared
to conventionally cast (CC) and directionally solidified (DS)
Mar-M 247. These data were taken from various Cannon
Muskegon brochures and the Metals Handbook.
9 If some grain boundaries are not perfectly aligned with the solidifica-
tion direction, creep cracks may initiate at these boundaries where
they intersect a free surface.
9 The removal of grain boundary strengthening elements, including C,
B, Zr, and Hf, might improve the fatigue properties by elimination
of MC-type carbides and could increase the incipient melting tem-
perature and therefore the creep resistance, because these elements are
melting-point depressants. The increase in the melting point permits
solutioning of large amounts of coarse ),' which later precipitates as
fine 7', enabling realization of the full strength potential. Addition
of Re has also proved a boon in improving the creep strength by
partitioning to )/. The improved creep strength realizable from single
crystal alloys over DS and conventionally-cast materials is illustrated
in Fig. 1. The alloy Nasair 100, which is a single crystal derivative
of Mar M 247, shows a 22~ (40~ temperature increase capability
with respect to the conventionally-cast Mar M 247, and about 17~
(30~ with respect to DS Mar M 247.
9 In the absence of grain boundaries, more flexibility in alloying might
be achieved that would result in an optimum balance of creep-rupture
strength and oxidation and hot corrosion resistance. Development of
leaner alloys also improves castability.
Single crystal blades (alloy PWA 1480) were initially put into commercial
service in 1982 in Pratt and Whitney's engine in a Boeing 767 aircraft and
Airbus A310. Howmet, the market leader in SC casting for aircraft compo-
nents, has shipped more than 10,000 single-crystal castings. All major
aircraft engine manufacturers have developed and applied new SC alloys in
recent years. The only use of SC alloys in land-based turbines to date has
been the use of CMSX-4 alloy in Solar Industrial Turbine's Mars T-14000
engine in 1990.l~ The application of single crystals to large land-based utility
turbines has, however, lagged behind for several reasons.
First, if SC alloys are to be used for industrial gas turbines, more
corrosion-resistant alloys must be developed. The alloys reported in the
literature so far are low-chromium compositions with adequate corrosion
resistance for aircraft turbines, but not for industrial turbines.
A second and more severe problem for industrial turbine application is
the scale-up to larger sizes. Problems will be encountered in two areas:
(i) Single-crystal casting technology relies on the existence of a thermal

gradient which is typically 7~ (320~ twice as large as in DS
casting. H The larger the blade size the more difficult it becomes to establish
such a high gradient. If the gradient is too small, casting defects such as
freckles and equiaxed grains occur. Material cast under lower gradients will
have inferior properties, even if the casting defects mentioned above are
avoided. One reason is that the dendrite spacing depends on the gradient.
Low gradients result in large dendrite spacings which are difficult to solution-
ize, and cause inferior ),' structures. 12 Another reason is that a higher level
of porosity is to be expected which will affect particularly fatigue strengh. ~3
Some of the problems encountered with low gradients can be overcome by
using lower growth rates. This would lead, however, to lower throughput
rates and higher cost.
(ii) The combination of the high superheat temperatures of above

1500~ (2732~ required to obtain suitable gradients, the long periods of
contact between metal and mold wall, and the high concentration of reactive
elements can lead to considerable metal/mold interaction. At the same time,
the mold material is required to have sufficient strength to support the weight
of the melt. Thermal expansion coefficients of the mold and the metal have
to be matched in order to avoid problems due to thermal stresses during
cooling. All this makes the mold technology rather critical. The problems
will become more severe in industrial castings, since the weight of the melt
is larger and the furnace times are longer.
Nevertheless, it is expected that single-crystal airfoils will become a standard

feature in large industrial turbines within the next few years. It is worth
noting that although the idea was reported as early as 1968, the benefits
were generally appreciated, and both Pratt and Whitney and General Electric
engaged on a considerable in-house research effort, it is only within the last

few years that DS components have become widely used; and SC compo-
nents are still not "bill-of-materials" on many engines. There has been much
discussion recently of the accelerating pace of the transfer from research to
practice, and in some cases periods like three years have been suggested: it
has to be appreciated that in the field of advanced materials the interval
between research and practice is still quite long.
Oxidation and Corrosion

In the early days, the superalloys used were all high in chromium, and
formed protective Cr203 scales. However, the suitability of chromia scales
diminishes as the temperature rises, particularly in high-velocity gas streams,
because of the further oxidation to the volatile species CrO3. However, the
alloy developments for nickel-base superalloys resulted in an increase in the
A1 content, and several of the earlier high-strength alloys were capable of
forming A1203 protective scales, which are much more suitable for high-
temperature applications. Associated with this was a decrease in the chrom-
ium content, and these alloys proved to be sensitive to a form of accelerated
oxidation which was associated with the deposition of an alkali metal sulfate
on the airfoil surface. This type of attack is called hot corrosion. Because
of the presence of sulfur in the deposit, and the presence of sulfides in the
corrosion product, the attack was also referred to as sulfidation, but this
term should be kept for those reactions where reaction with sulfur is the
major process. The first type of hot corrosion reported involved only sodium
sulfate, and existed over a range of temperatures between the melting point
of the deposit and its dew point. This is now called Type I hot corrosion.
Later, another form was observed, initially in marine applications at part
load, and it was originally termed low-temperature hot corrosion. This turns
out to be associated with the presence of a molten sulfate which involves a
transition metal (usually cobalt) as well as sodium. This complex sulfate is
not very stable, and its stabilization requires a significant partial pressure
of SO3. The range over which the corrosion appears is between the melting
point of the salt and its dissociation temperature. This form of attack is now
called Type II hot corrosion.
The three processes: oxidation, Type I hot corrosion, and Type II hot
corrosion, represent significant problems for the durability of the gas turbine.
The relative importance of the processes depends on the application and the
siting of the turbine. In many cases the local concentrations of alkali-contain-
ing species in the fuel or the intake air are sufficiently low that only oxidation
need be considered, and the alumina-forming superalloys may be adequate.
For other circumstances, the salt deposition is not sufficient to cause severe
hot corrosion, but must be considered. Alloys have been developed which
will perform well under these conditions: the cobalt-base alloys X-40 and
FSX-414; and the nickel-base alloy IN 738 are of this class, and have been
the materials of choice for industrial gas turbines since 1970 (there are some
other alloys in this group). However, there are other conditions where the
salt intake is so great, even if only transiently, that even these materials are
inadequate.
The design of corrosion-resistant superalloys involves a sacrifice of some
strength, and some turbine designers have preferred to treat the strength
and the corrosion resistance as separable entities, using a high-strength alloy
for the main body of the airfoil, and then applying a corrosion-resistant
coating to the surface. Additional protection for the more corrosion-resistant
materials is conferred by using a coating, and thus most high-temperature
vanes and blades have been coated for over 20 years.
Coatings
The earliest coating was aimed at increasing the surface content of

aluminum, since even the alumina-forming superalloys contain barely
enough aluminum to maintain a protective scale. Alumina scales tend to
spall on cooling, and then hopefully a replacement scale is formed on reheat-
ing; the lifetime is thus related to the number of heating and cooling cycles
and the magnitude of the aluminum reservoir in the substrate. Processes to
form an aluminum-rich layer on a metal surface existed well before the
development of the modern gas turbine. The technique used for much of
the early period was pack aluminizing (sometimes called pack cementation),
in which the component to be aluminized was placed within a bed consisting
of an inert powder material (usually alumina) mixed with a relatively small
amount of aluminum or an aluminum-containing alloy, and a constituent
called the activator, which is a halide such as sodium chloride. The pack is
contained within a metal box (retort) and heated for a fairly long time at a
fairly elevated temperature, depending on the alloy, the thickness of the
aluminized layer required, and so forth. Until quite recently, the majority
of components in service were pack aluminized. This process is an example
of chemical vapor deposition (CVD), and some recent developments have
been made by addressing it as a CVD process, and in some cases physically
separating the step of forming the vapor species, which transports the alumi-
num to the component surface, from the surface itself. This permits much
better chemical control.
In 1972, there was a major advance, 14 in which platinum was incorpor-
ated in a diffusion aluminide. There are various ways of doing this, but the
most usual method is to electroplate a thin layer of platinum onto the
component, and then aluminize in the usual way. Currently, the most fre-
quently used modified aluminides are RT-22 (this is a Chromalloy designa-
tion; other companies have similar coatings with different designations) and
RT-44, which contains rhodium as well as platinum and is used for cobalt-
base superalloys.
Pratt and Whitney initiated a program to develop a completely different
approach to coatings, in which the coating was overlayed onto the substrate
by evaporating the metal components of the coating from a source using an
electron beam, and allowing the vapor to condense on the substrate. This
is called electron beam physical vapor deposition, EB-PVD. Working with
Airco Temescal, by the late 1960s they had developed a range of MCrA1Y
overlay coatings, where M is Fe, Co, Ni, or a combination of these. 15 A
typical composition is Co-15 to 20% Cr 12% A1 0.1 to 0.9% Y; the role of
the yttrium is to restrict the spallation of the protective oxide on thermal
cycling; the chromium offers resistance to hot corrosion.
The effort devoted to the development of coating compositions has been
as energetic as that for the base alloys. A wide range of coating compositions
is available from vendors: a recent EPRI report briefly lists a number of the
more common 16coating systems. The most recent development has been the
introduction of rhenium, akin to its introduction into the base alloys. It is
believed to improve the performance, but as yet there appears to have been
no explanation of the mechanism of the effect.
As mentioned before, single-crystal airfoils present a new set of prob-
lems for coatings, and it is hoped that alloy compositions can be developed
which do not require coating, at least for the less severe conditions.
The most recent development in coating technology is the use of coat-
ings with low thermal conductivity (thermal barrier coatings, or TBC) to
maintain a relatively low metal temperature at high inlet gas temperatures,
and to reduce the amount of cooling air required. The most successful coat-
ing of this type is zirconia (ZrO2), where the cubic form of zirconia is
partially stabilized by yttria (Y203), or magnesia (MgO). The coating is
applied, usually by plasma spraying but also by EB-PVD, over a bond coat
which is usually an MCrA1Y. Currently, TBCs are used on combustors,
transition pieces, parts of the nozzle guide vanes, and the platforms of the
blades: some Pratt and Whitney JT9-D aircraft turbines have been flying
since 1989 with TBCs on the rotating blade airfoils for evaluation purposes.
An important problem with TBCs concerns the bond coat, and in par-
ticular the oxidation and hot corrosion of the bond layer. The TBC itself is
generally not impermeable: ZrO2 supports anion (oxygen) transport, and it
is usually arranged for the ceramic itself to contain a network of microcracks
as a way of overcoming the problems associated with the differences in the
coefficients of thermal expansion of the ceramic and the substrate. This
Current Limitations of High-TemperatureAlloys in Practical Applications 277
means that oxygen or other corrodent species may reach the bond coat-
TBC interface under conditions which may easily lead to low oxygen activity
environments, and which can result in continued oxidation of the bond coat,
and even accelerated local corrosion. Much attention is currently focused
on understanding how changes at the bond coat-TBC interface influence
the mode of degradation of the coating system, and on the possible incorpor-
ation of oxygen diffusion barriers in the TBC.
MATERIALS IN LARGE COAL-FIRED BOILERS

Much of the subsequent material on the structure of boilers is a very
simplified extraction from "Steam: Its Generation and Use. ''17
Approximately 65% of the electricity generated in the United States is
produced by generating stations based on the Rankine cycle, in which steam
is generated in a boiler, expanded through a steam turbine which drives a
generator, and condensed before being returned to the boiler. This is thus
an indirectly-fired closed-cycle system; the compression is (in effect) pro-
duced by the boiling. In detail, the water is preheated as it returns from the
condenser by steam tapped from the turbine, and enters a horizontal tubular
heat exchanger in a pass of the boiler where the combustion gas is passing
downwards prior to exiting the system (this is called the economizer). From
the economizer, the preheated water enters a (usually) vertical tubular heat
exchanger which forms the walls of the combustion chamber, and boils; the
relative fraction of steam-to-water rises as the fluid rises through the walls.
In drum-type boilers, the tubes are manifolded at the top of the walls into
a large drum, which separates the steam from the water. The water returns
to the bottom of the wall and recirculates, and the steam passes into a
horizontal tubular heat exchanger which is located above the economizer.
This is called the primary superheater, and is heated by convection from the
flue gas. From this, the steam passes into a vertical tubular heat exchanger
hanging in the roof of the combustion chamber: these tubes are arranged
in a flat array called a platen, and the heat exchanger consists of a number
of platens in parallel which are manifolded into a header. This heat
exchanger, the secondary or finishing superheater, receives heat by convec-
tion from the flue gas and, in some designs, by radiation from the combustion
zone. From the header, a main steam line carries the superheated steam to
the turbine. The first part of the turbine is called the high-pressure (HP)
turbine, and the exhaust from this returns to the boiler where it is reheated
in a sequence of heat exchangers. The finishing reheater is again manifolded
into a header, from which a reheat system line carries steam back to the
second section of the turbine, which is called the intermediate-pressure (IP)
turbine. Generally, the exhaust from this enters directly into the third section
of the turbine, which is called the low-pressure (LP) turbine. However,

sometimes there may be a second stage of reheat between the IP and
the LP.
On the fireside of the boiler system, coal is pulverized to 70% passing
through a 200 U.S. standard sieve (75/lm) or better. This is transported by
primary air at 54-93~ (130-200~ to the burners, which are in the lower
part of the combustion chamber, from perhaps 10 to 20 m (35 to 65 ft)
above the bottom of the unit. Secondary air preheated to about 316~
(600~ is supplied by the forced draft fans and mixed with the pulverized
coal in the throat of the burner. A single burner is typically in the range
15-90 MWth, so that a 500-MWe boiler could have from 20 to 100 burners.
The objective is to form a fireball in the combustion chamber enclosure
separated from the walls. Heat is transferred from this fireball to the water-
walls largely by radiation, with a maximum flux to the walls of the order of
0.3-0.4 M W / m 2 at a level just above the top of the burners, falling to about
0.1-0.2 M W / m 2 at the top of the combustion chamber.
The gas temperature immediately above the fireball is typically of the
order of 1538~ (2800~ and that impacting the leading tubes of the pend-
ant finishing superheater is some 111 ~ (200~ lower. At this location, the
gas stream turns into a horizontal pass, containing a number of vertically
oriented heat exchangers. The gas temperature entering this pass is approxi-
mately 1093~ (2000~ and the mode of heat exchange is increasingly
convective.
All of these temperatures are approximate, and depend on the furnace
design, the fuel type, and so forth; and there may be large variations across
the face of the superheater, for example.
After the horizontal pass, the flue gas turns into a downward convection
pass, which contains the primary superheater and the economizer, both of
which are typically horizontal tube banks. From there, the gas enters the
air heater, which preheats the secondary combustion air, and then passes to
the environmental control systems and finally to the stack.
This brief description is of a recirculating, single reheat, subcritical
boiler which represents the majority of the units in the United States. Typ-
ically, the maximum steam pressure, that of the steam entering the high-
pressure (HP) turbine, is 16.6 MPa (166 bar; 2400 psi), and the temperature
is 538~ (1000~ The pressure in the reheater is close to 3.8 MPa (38 bar;
550 psi) and the exit temperature is 538~ (1000~ again. The boiling point
of water at 16.6 MPa (2400 psi) is 349~ (660~
An alternative method is to operate the system above 22.1 MPa
(221.2 bar, 3208.2 psi) which is the critical point for the water/steam system.
At pressures above this, water does not form a two-phase steam/water
mixture on boiling: the system forms a single-phase, turning continuously
from a fluid resembling water to a fluid resembling steam: in a glass tube

supercritical boiling is indicated by the disappearance of the interface
between the liquid and the vapor. In this case, there is no need for a steam
drum, and there is no recirculation. Supercritical once-through units in the
United States operate at 23.8 MPa (238.5 bar; 3500 psi). The superheating
process is the same, and the main steam temperature is again 538~
(1000~ the reheat is also essentially the same, but more frequently there
are two stages of reheat. Since a number of references in the subsequent
part of this paper are to work performed in the U.K., it should be pointed
out that the steam temperatures there are a little higher, typically 565~
(1049~
The efficiency of a large steam plant depends essentially on the difference
between the temperature of the steam on entry to the HP turbine and the
temperature of the steam-water mixture exciting the low-pressure (LP) tur-
bine. This last temperature is determined by the back-end pressure, and is
a function of the condenser. For a modern boiler the back-end pressure
is typically 400 Pa (4 x 10 . 3 bar; 58 x 10.3 psi) or so, corresponding to a
saturation temperature of 30~ (86~ assuming of course that adequately
cool water is available to cool the condenser. There is little flexibility at this
end of the system, so that further improvements in efficiency require an
increase in the maximum steam temperature. The steam pressure does not
in itself affect the efficiency directly, but higher pressures allow the system
to be smaller for a given power, and permit more efficient steam turbines to
be built. From 1905 to 1957, the main stream temperatures and pressures,
the size of the units, and the overall power plant efficiency, all increased
progressively. The maximum in the steam conditions was reached with the
double-reheat, supercritical units at Philo [30MPa, 621/565/538~
(4500 psi, 1150/1050/1000~ and at Eddystone [34.5 MPa, 649/565/
565~ (5000 psi, 1200/1050/1050~ the latter unit attained a coal pile-
to-bus bar efficiency of 42~ (although, it should be remembered, without
flue gas desulfurization).
However, the industry has retreated from these advanced conditions to
the values given above. The reasons are not altogether clear: the greater
expense of the plant, because of the larger amount of high-alloy austenitic
steel that had to be used, a perception of increased unreliability, through
other causes such as heat checking in the main steam valves, attributable to
having to make these heavy section components from austenitic steels with
relatively poor thermal conductivities; an increased incidence of tube fail-
ures; and a decrease in unit flexibility have all been suggested. In part, the
increase in tube failures was attributed to fireside corrosion. In the last few
years, there has been a renewal of interest in advanced steam conditions in
the United States of America, Japan, and Europe. EPRI sponsored two
system studies 18'19 to identify the most desirable configuration, the possible
benefits, and those areas which presented problems or would require addi-
tional development; and following these a development plan was
generated. 2~ Later, a workshop21 was held to report on the progress of this
study22 and of efforts elsewhere in the world. At more or less the same
time, the U.S. Department of Energy assessed the materials requirements
for advanced steam cycle systems23 and conducted research into materials
for superheaters and reheaters for advanced steam conditions.24
Following these initial studies, EPRI selected intermediate conditions
for its "state-of-the-art power plant" (SOAPP) 25 which became the subject
of much more detailed development, aimed at defining a realistic option for
utilities in the relatively near future. An important alloy development for
these advanced steam concepts was the improvement in the Fe-9%Cr-1%Mo
steels, which led to the T-91 and P-91 steels. These high-strength ferritics
allowed heavy-section components to be designed using solely ferritic mat-
erials, with their higher thermal conductivity.
Materials Issues in Pulverized Coal Fired Boilers

The typical utility pulverized coal fired boiler and the associated systems
is a very large structure indeed, and there are a large number of materials
issues. In fact, there is a limited range of materials that can be used for
boiler tubes, and all such alloys must be qualified in accordance with the
ASME codes. For the highest-temperature components in the boiler, which
are the finishing superheater tubes, the finishing reheater tubes, and the pipes
which carry the steam to the turbine, the issues are related to creep and to
oxidation and corrosion. The relatively cooler evaporator tubes which are
in the waterwalls facing the combustion zone nevertheless may also suffer
corrosion damage. The still-cooler economizer tubes in the boiler downpass
do not experience significant corrosion, but may experience erosion from
the fly ash; under some circumstances the superheater and reheater tubes
may also experience erosion. Oxidation can be an issue on both the fireside
and the steam-side of tubes. In this paper, only superheater and reheater
fireside corrosion and waterwall fireside corrosion will be discussed because
of limitations on space; but it should not be concluded that these are the
only, or even the most important materials issues in pulverized coal-fired
boilers.
To help in putting these issues in context, the general issue of boiler
tube failures will be briefly mentioned.
Causes of Boiler Tube Failures

Boiler tube failures (BTF) are the leading cause of forced outages and
availability losses in fossil-fueled power plants. 26 Recent statistics compiled
by the North American Electric Reliability Council 27 indicate that BTFs are
responsible for approximately 70% of the forced outages and 50% of the
lost availability of fossil-fueled power plants. Twenty-two distinct BTF
mechanisms have been identified as a result of cooperative research between
the U.S. utility industry through EPRI in cooperation with the major boiler
manufacturers (RP- 1890-1). The major failure mechanisms of boiler tubing
are
A. Stress rupture (short-term overheating; high-temperature creep; dis-
similar metal welds)
B. Water-side corrosion [caustic corrosion; hydrogen damage; pitting
(localized corrosion); stress corrosion cracking]
C. Fireside corrosion (low temperature; waterwall; coal ash; oil ash)
D. Erosion (fly ash; falling slag; sootblower; coal particle)
E. Fatigue (vibration; thermal; corrosion)
F. Lack of quality control (maintenance cleaning damage; chemical
excursion damage; material defects, welding defects)
The two failure mechanisms of most relevance to this symposium are
waterwall fireside corrosion, and fireside corrosion of the superheaters and
reheaters ("coal ash" and "oil ash" corrosion in the above listing). Of these,
fireside corrosion of the superheaters and reheaters has been relatively
uncommon in U.S. utility experience in recent times, but it has been studied
in very great detail over the years.
Waterwall Fireside Corrosion in Coal-Fired Boilers
Rapid wastage of the waterwalls is sometimes experienced in coal-fired

boilers; it is normally associated with a failure to establish the combustion
zone properly in the center of the furnace ("flame impingement on the
walls") with the result that a region of local low oxygen activity is present
at the waterwall surface. The high heat flux means that a slag layer develops
with a molten outer surface, although the metal surface temperature is nor-
mally quite low. Reid 28 comments that the first real attempts to investigate
external corrosion of wall tubes began in the 1940s. Severe metal loss was
occurring on wall tubes beneath slag deposits related to the flame pattern
in slag-tap furnaces. Reid notes that at the time of writing (1971) there was
still no general agreement as to the mechanism of the reaction, and in spite
of a considerable amount of work in the intervening 20 years that is still
true. Better control of the fuel/air distribution in the furnace, coupled with
accumulated experience with burner design and location, and the trend in
recent years to dry-bottom furnaces, have eased the problem considerably.
Nevertheless, Manny and Natanson 29 reported recently that metal wastage
rates of 30 35 nm/h (10-12 mil/yr) are still occurring, compared to the

maximum of 8 nm/h (3 mil/yr) that would be expected based on normal
oxidation. The early studies, reported by Reid, Corey and Cross, 3~ made it
clear that the metal surface temperature in regions of severe attack did
not exceed 375~ (707~ and that there was no difference in temperature
between severely attacked tubes and other nearby tubes which appeared to
suffer no attack. Corrosion may occur at metal temperatures as low as 315~
(600 ~ F).
The slag layer on the wall contains particles of unburnt carbon and
particles of unoxidized pyrite, FeS2. In the earliest work, it had been postula-
ted that the local "reducing conditions" might be a factor because volatile
iron carbonyls might be formed. This was quickly discounted, and the early
American work described by Reid concluded that the low-oxygen activities
were unimportant and that the alkali iron trisulfates were the important
corrosive species: the model presented in the section on superheater corro-
sion in coal fired boilers was, indeed, originally developed to explain wall
tube corrosion. The low local oxygen partial pressure would appear to mili-
tate against the development of high local SO3 partial pressures and thus
reduce the probability of formation of the trisulfate, but the stabilities of
complex sulfate phases under these conditions have not been studied in
detail. In addition, the lowest reported melting points of these phases are of
the order of 550~ (1022~ and it seems unlikely that other components
could depress them below 500~ (932~ Alkali iron pyrosulfate has been
suggested as the responsible molten species, because of its lower melting
point, but this is even less likely since the partial pressure of SO3 required
to stabilize it is even higher: all in all, it seems unlikely that these complex
sulfate species could be stable in the low-oxygen-activity environments.
Because of extensive furnace wall corrosion experienced in some large
pulverized coal boilers in the United Kingdom, this problem has been exten-
sively studied by what was then the U.K. Central Electricity Generating
Board (CEGB). The earlier work has been summarized by Cutler, Flatley
and Hay31; and a series of papers was presented in the conference edited
by Meadowcroft and Manning. 32 The initial view developed by the CEGB
investigators had been that chlorides play a key role in the reaction. The
low oxygen potential conditions were believed to result in the surface release
of "volatile chlorine and sulfur gases." The active chemical species respon-
sible for the high corrosion rates were believed to be HC1, H2S/SO2 and
CO. Laboratory experiments in gaseous environments suggested that HC1
reacts with the outer oxide grain boundaries of previously formed protective
scale, creating microchannels through which (eventually) HC1 gains access
to the metal-scale interface. There, a volatile iron chloride is formed which
escapes into the bulk furnace gases, where it is oxidized, reforming HC1.
~ ~/ ~~/ / - - FeS lamellae
~,f- Fly ash spheres
~,~'~g
,2/--oa Unburnt
lc'os coal
Metal ( Fig. 2. The general structure of the corrosion
scale formed on furnace wall tubes: intermedi-
ate case. The scale thickness is 200 300/ira; the
corrosion rate is approximately 300 nm/h, In
somewhat milder corrosion conditions there is
Fe 3~ matrix
also intergranular penetration into the sub-
strate. (After Cutler, Flatley and Hay31).
However, it is clear from boiler experience that an important reaction

product is iron sulfide, FeS. The CEGB differentiated three different struc-
tures corresponding to three reaction regimes: in the first, corresponding to
a corrosion loss of 200 n m / h (69 mil/yr), a thick scale was formed: the outer
layer was porous Fe203 mixed with ash; the inner layer had an Fe304 matrix
with FeS islands embedded in it; the metal exhibited intergranular internal
attack. The second involved the formation of a thinner scale: the inner layer
had extensive sulfide lamellae, and the outer layer was less thick. There
was no intergranular attack of the metal: the rate of metal recession was
approximately 300 n m / h (103 mil/yr) (Fig. 2). 31 The most rapid corrosion
(600 n m / h ; 207 mil/yr) corresponded to the formation of a thin scale which
was almost entirely FeS, with ash particles embedded in it. There was a thin
inner layer of Fe304, which may be porous or laminated; there was no
internal attack of the metal.
More recent evaluation of the corrosion in practice has resulted in a
discounting, to some extent, of the role of chlorine except in the most severe
cases, since it is now believed that the low-oxygen-activity environment in
the presence of sulfur (and, perhaps, carbon) is sufficient to account for
most of the corrosion.
Japanese investigators note that some corroded wall tubes exhibit deep
corrosion penetrations in the form of parallel grooves normal to the tube
axis with a spacing of the order of 1 ram: sulfur prints show clearly the
existence of sulfides associated with these penetrations. French 33 has also
reported these features. Their origin is believed to be related to the inter-
action of thermally induced alternating stresses and the corrosive environ-
ment. This phenomenon has been discussed recently by Dooley, 34 who
comments that this is an issue primarily with supercritical units: most of the
155 supercritical units in the United States suffer from this failure mecha-
nism. The cracking originates from the fireside surface in regions of high
heat flux, 35 and has been referred to by a variety of names: circumferential
cracking, horizontal cracking, transverse cracking, craze cracking, elephant
hiding and alligator-skin cracking. Unless failure occurs, cracks are very
often not detected unless a careful and extensive inspection is performed.
Very often the susceptible areas are overheated and suffering from excessive
fireside corrosion.
A comprehensive EPRI project has been undertaken for the last three
years to monitor these areas for temperature and strain (fireside and
coldside), cycle chemistry and flue gas environment to determine the critical
and overriding parameters. 36The root cause of the cracking and overheating
is due to a combination of the internal deposits raising the peak tube tem-
perature and the fireside slag shedding, which may be driven by sootblowing
or may occur on a random basis, depending on location in the boiler. The
internal deposits (Fe304) are often "rippled." Similar overheating and fail-
ures have occurred in other countries, 37 where rippled magnetite formation
on the waterside surfaces has been directly related to elevated tube tempera-
tures in the high heat flux areas and to boiler pressure drop loss problems.
The influence of internal oxide deposits on the fireside metal surface tempera-
ture is an important factor, which the early work completely neglected.
Obviously, a fireside deposit reduces the metal surface temperature toward
the water/steam temperature inside the tube; but adequate heat transfer can
only be obtained if this effect is small, or if the wall deposits frequently
detach.
The solutions to the waterwall corrosion problem include: finer grinding
of the coal to accelerate combustion, improved burner design and mainten-
ance; and bleeding air along the walls to try to keep the local environment
oxidizing. For the circumferential cracking problem, oxygenated water treat-
ment can help by greatly decreasing the magnetite deposition on the water-
side surface, and methods of reducing the peak heat flux locally, such as the
maintenance of slag cover, or the application of refractory coatings, may be
useful in some cases.
However, where severe corrosion is encountered, a materials solution
appears to be the most attractive. The CEGB has conducted extensive tests
with coextruded tubes, 32'38 in particular Type 304 stainless steel outside a
carbon steel inner layer, or Type 310 over a carbon steel inner layer. In both
cases the outer layer was 1.75 mm (69 rail) thick and the inner layer 6.55 mm
(0.258 in) thick. Both materials had, at the time of the report, accumulated
27,000 h in a 500-MWe boiler burning a 0.3% C1 coal. The corrosion rates
were between 4 and 10 times lower than those of carbon steel in the same
boiler: the maximum rates were 77 nm/h (27 mil/yr) for the Type 304
Current Limitations of High-Temperature Alloys in Practical Appfications 285
combination and 55 nm/h (19 mil/yr) for the Type 310. However, it should
be pointed out that with coated systems the important quantity is not the
corrosion rate, but the life of the coating: since the coatings were only
1.75 mm thick, these corrosion rates would remove them after 2.5 years in
the first case and 3.6 in the second. It was noted that, because of the low
temperature, the full protection that one might expect from a developed
Cr203 layer was not obtained, and a suggested improvement was to increase
the chromium content still further by using an IN 671 outer layer. Diffusion
aluminizing has been successful in some cases. A three-layer plasma spray
coating, involving an initial exothermic layer to develop a good bond with
the substrate, an intermediate layer to provide an aluminum (and perhaps
also a chromium) reservoir, and a final layer to seal the porosity, has had
some success. The durability of coatings, and their freedom from local
defects, is still a matter of doubt, however.
Fireside Corrosion of Superheaters and Reheaters

Fireside corrosion is associated with the formation of ash deposits on
the tubes. Crossley39 reported that work by the U.K. Fuel Research Station
in the 1940s had indicated that the external fouling of boilers in the U.K.
was connected with the alkali and SO3 contents of the deposits. It was
believed that alkalis existed in coals in two forms: chlorides and complex
silicates (this is in fact an oversimplification: alkali chlorides are not common
in coals, but for this argument the point is not important). The chlorides
could be expected to volatilize readily during combustion, but the silicates
were expected to retain alkali in the ashes. Thus, it was found convenient
to use the amount of chlorine in the coal as the indicator of the volatile
alkalis, to distinguish the alkali available to participate in fouling from that
in the complex silicates. As a consequence, the determination of coal-chlor-
ine content has been an important item in the ultimate analysis of coals in
the United Kingdom since that time. The most common superheater deposits
that led to outages were typically alkali-bonded, and so a correlation was
sought between the rate of fouling by alkali-bonded deposits and the amount
of chlorine in the coals. A survey indicated that there appeared to be a good
correlation between the rate of fouling and the chlorine content in the coal
for 72 power stations with stoker-fired boilers, whereas for 14 stations with
pulverized coal-fired boilers, there was little fouling due to alkali-bonded
deposits, and no relationship of fouling with chlorine in the coal. The relative
immunity to bonded deposits of pulverized coal (PC)-fired boilers was attri-
buted mainly to the very large amount of fly ash from PC firing in excess
of the amount of binding agent required to produce a bonded deposit.
Although PC-fired boilers appeared to be relatively immune to fouling
with coals containing up to 0.5 wt% chlorine, the rate of fouling when this
immunity had broken down was appreciably faster than in boilers fired by
mechanical stokers. Fouling trials carried out on coals with various levels
of chlorine (up to 1.0 wt%) indicated that no boilers fouled when burning
coals of very low chlorine content, but all boilers fouled when burning coals
of very high chlorine content. Between the extremes of chlorine content,
fouling was accelerated or promoted by increasing the amount of sulfur in
the coal.
By the time the hot flue gas reaches the radiant superheater it has cooled
into the range 1200 to 1000~ (2192 to 1832~ and the entrained ash
would be expected to be largely solid. The proposed effect of sulfur was that
relatively low amounts of SO3 lead to the formation of normal alkali sulfates
as binding agents, whereas increasing the amount of SOs leads to the produc-
tion of the corresponding acid sulfates which are considerably more fusible
than the normal sulfates. The amount of ash from the coal also was of
considerable importance, since it appeared that the ratio of ash to binding
agent was a major factor in determining whether bonded fouling deposits
could form.
There have been several theories for the buildup of the deposit. The
early theories have been summarized by Bishop4~
(i) Alkali metal salts in the vapor phase condense on the tubes to
form a sticky layer ("flypaper") which collects impacting particles
of fly ash.
(ii) The initial deposit consists of powdery fly ash; the insulating effect
of this ash results in the outer layers of the deposit becoming hotter
than the inside, and this temperature gradient allows a partial
decomposition of sulfates in the hotter parts, with the SO3 so
formed diffusing toward the colder metal surface. An inner dense
alkali sulfate-rich layer forms.
(iii) Alkal metal or alkaline-earth oxides are deposited on the surface,
and are then converted to low-melting point sulfates and pyrosul-
fates by reaction with the SO3 in the bulk gas phase, and perhaps
with other elements in the deposit.
(iv) Alkali chloride vapors from high-chlorine coals, or alkali hydrox-
ide vapors from low-chlorine coals condense upon the tubes, and
are subsequently converted to sulfates.
(v) Silicon compounds such as SiS, SiSz, or SiO are evolved as vapors
from silicate minerals during combustion, are then deposited as
fine aerosol particles on the tube surface, and rapidly oxidized to
silica.
(vi) Molten and partially molten ash particles in the hot gas stream
impact the cold metal surface, and freeze in place.
Flue gas stream
~
~, Friable ash
deposit
~-1~ [ Iron-rich, hard

~:.~,k, ~"red slag"
~ W h i t e , alkali-
~ Hard black
Fe304 scale
Fig."3. Deposits and corrosion area for a. 41typical

reheater tube. (After Nelson and Cam ).
Bishop also identified a number of factors which could contribute to

fouling. These include
(a) The presence of relatively minor amounts of molten material, usu-
ally alkali-metal-salt-rich, on the surfaces of the fly ash particles
themselves, or the tubes
(b) The presence of very fine particles (aerosols) of alkali salts, usually
water-soluble, which encourage sintering of the fly ash
(c) The presence of acicular crystals of oxide which project from the
oxidized tube surface, trap ash particles, and encourage the build-
up of deposits
(d) An irregular tube surface, which is likely to influence collection
during the first few hours of deposition
Generally, it appears that a white deposit is formed first, on both the
leading tube surface (that facing the gas stream) and the trailing surface.
This white deposit is largely alkali sulfate. Later, an ash deposit forms,
largely on the leading surface. Not all deposits, by any means, result in
enhanced fireside corrosion; but a deposit is essential for accelerated corro-
sion. The deposit on a corroding tube has the general appearance shown in
Fig. 3, which is essentially that of Nelson and Cain. 41 The black inner layer
is iron oxide, essentially Fe304 ; the white layer contains significant amounts
of alkali sulfates, together with many of the ash constituents but relatively
little iron; the "red slag" layer is high in iron, low in alkalis, but with sulfate
FLUE GAS DIRECTION F'LUE GAS DIRECTION
/
/ ' ~ F R I A E , LELAYERC / ~
l,OOO. ISOT ERM
/ ~NIN~h,.~--_MOLTEN , E D ~ \
10:~5"r ISOTHERM,-~ LAYERB
/.~ ~~ ~ ~ /~~il~L~. MOLTENWHITE
" ~ L O O S E L Y r ~ ~ " I " - LAYER D
l~l;~ V / ~'/'-/; / ,~//."~'~,~ BONDED L AYER A J l ; ~ J V ' / / / / / / / / / / / / / ~ IB~l
~~.,i \. v /
Fig. 4. The effect of steam temperature on deposit structure. (After Borio, Plumley and
Sylvester42).
content intermediate between that of the ash and that of the white layer.
When dissolved in water, both the white layer and the red slag layer give
acid solutions; the solution derived from the outer ash is essentially neutral.
Borio, Plumley and Sylvester 42 have described the structure on tubes with
two different steam temperatures, as shown in Fig. 4, and concluded that
the alkali-rich material was molten in the range of 590-700~ (1094
1292~ Figure 5, taken from "Steam, Its Generation and Use," issued by
Babcock and Wilcox, 17 shows the analysis of different regions of the deposit.
Figure 6, from Cutler and Raask, 43 shows the temperature distribution
through a superheater tube for a typical set of circumstances. This diagram
may be somewhat oversimplified. The overall heat flux to the superheater is
indeed of the order of 0.2 MW/m 2, but as is clear from Fig. 3, the thickness
of the insulating ash layer on a leading tube is greater at the front than at
the back. As a result, the heat flux will vary round the tube, being least
where the ash layer is thickest. Wastage takes place at the edges of the
deposit--the "five o'clock and seven o'clock positions"--where presumably
the heat flux is higher, and the situation may approach that shown in Fig.
4. In the limit, the metal temperature beneath the deposit will be closer to
the steam temperature as the heat flux falls, and the temperature of the
"alkali sulfate" layer shown in Fig. 4 will also be lower, by as much as
100~ (180~ However, the local SO3 partial pressure can be expected to
diminish from the thick part of the deposit to the thin part, and the inter-
action of the two variables, temperature and SO3 partial pressure in the
Gas Flow
2100F (1149C)
Outer Intermediate Inner

Layer Layer Layer
% by wt % b y wt %bywt
SiO2 23.5 23.3 7.6
A1203 14.0 11.5 1.7
Fe203 36.0 11.0 70.5
TiO2 0.9 < 0.1 < 0.1
CaO 1.3 < 0.1 < 0.1
MgO 1.3 1.1 <0.1
Na20 0.3 1.7 0.15
K20 2.9 13.5 1.3
NiO <0.1 <0.1 0.3
Cr203 < 0.1 < 0.1 7.0
SO3 7.3 27.5 10.0
CI 0.02 < 0.01 < 0.01
Water Soluble, % 9.0 45.4 9,0

pH 3.0 2.2 4.3
Excess SO3, % 0.5 11.2 11.8
Fig. 5. Analyses of a typical ash deposit from an 18Cr 8Ni superheater
tube. (From Stultz and Kitto17).
vicinity of the alkali sulfate-rich layer, will determine the location of the
maximum attack.
As has been pointed out in the discussion of hot-corrosion in gas tur-
bines, the alkali sulfates themselves are not molten in this temperature range.
Na2SO4 melts at 884~ (1623~ and K2SO4 at 1069~ (1956~ the two
form a continuous range of solid solutions with a minimum melting point
of 823~ (1530~ As pointed out earlier in the analogous situation for
waterwall corrosion, in the search for low-melting-point phases, early investi-
gators suggested the pyrosulfate (Na,K)2 $207 which melts at temperatures
of the order of 400~ (752~ but is unstable: it dissociates to its constituent
sulfates unless the partial pressure of SO3 is high. Corey, Cross and Reid 44
as early as 1945 had identified a phase--the alkali iron trisulfates,
Alkali
sulfate }
Iron- Flue gas
Metal Oxide rich l Ash (-~ 1000~
ash I
I
I 977
I // Temperature (~
652( ,-/
I,(
l/
,
Heat flux = 0.2 MW/m2
77
I
I 1
Fig. 6. The general temperature distribution through a
superheater tube, the oxide, and the deposit. (After Cutler
and Raask43).
(Na,K)3 Fe(SO4)3--which several later investigations suggested were impor-

tant in the corrosion. Cain and Nelson 45 showed that there was a minimum
melting point of 554~ (1029~ at a Na : K ratio of 2 : 3 (Fig. 7). In addition,
there are analogous alkali aluminum trisulfates: the pure salts melt at
approximately 650~ (1202~ but again there is a minimum melting mix-
ture at approximately 540~ (1004~ these melting points may be further
depressed by the presence of other constituents such as LizSO4. The alkali
iron trisulfates, like the pyrosulfates, are unstable and will dissociate to the
constituent sulfates unless there is a relatively high-local SO3 partial pressure;
Reid 28 remarked that they will dissociate at 540~ (1004~ unless the SO3
partial pressure is at least 25 Pa (25 x 10 -5 bar/3.6 x 10 -3 psi); this is, how-
ever, considerably less than would be required to stabilize the pyrosulfates.
The problem is then to show how the SO3 partial pressure can be
enhanced over the levels normally present in the furnace, which seldom
exceed 5 Pa (5 x 10 -5 bar; 7 x 10-4 psi). Krause, Levy and Reid 46 were able
to show experimentally that the SO3 levels immediately above oxidized metal
surfaces in the gas were considerably enhanced, presumably due to catalytic
oxidation of SO2. The more successful laboratory tests, such as those of
Kihara, Isozaki and Ohtomo 47 and of Rehn 48 have found it necessary to use
an atmosphere containing both SO2 and 02 passed over a catalyst. Rehn
used a gas containing 3.6% O2 and 0.25% SO2 ; the catalyst was Fe203, and
the equilibrated gas contained 50-80 Pa (50 80 x 10 -5 bar; 7 - 12 x 10 3 psi)
S03.
1200
I I I I l
h 1150 J
IIO0
Q.
E
Joso
~ooo I I I I
0 2 4 6 8 --~
No-- 8 6 4 2 0
Molor Rotio of K 3 Fe(S04) 3 to No 3 Fe(S04) 3
Fig. 7. Melting points as a function of composition in the system
Na3Fe(SO4)3-K3Fe(SO4)3. (After Cain and Nelson45).
The temperature dependence of the corrosion is usually described in

terms of a "bell-shaped curve." Borio, Plumley and Sylvester 42 show the
general form of the corrosion for austenitic stainless steels in laboratory
tests in Fig. 8, and also showed that the corrosion range corresponded fairly
closely to the range within which a 1:1 N a : K alkali-iron trisulfate was
molten or sticky; the maximum corrosion rate corresponded to the maxi-
mum temperature at which the salt was wholly molten. Cutler and Raask 43
also related the decline to the decreasing stability of the low-melting-point
complex, and included the contribution of the heat flux. For a given metal
temperature, the corrosion rate increases with increasing gas temperature. 49
This could be related to the migration of SO3 or the liquid sulfate species
in the temperature gradient.
Although the "bell-shaped curve" is generally regarded as describing
the temperature dependence of the corrosion, Rehn also commented that
the rapid decrease in corrosion rate at temperatures above that of maximum
attack, and the actual maximum itself, may well be artefacts of the experi-
mental technique used to determine them. In particular, the location of the
maximum will depend on the local SO2/SO3 concentration; and that if a
molten alkali iron trisulfate is formed at the lower temperature, the tempera-
ture can be raised and rapid corrosion will continue, whereas the corrosive
liquid will not spontaneously form at the higher temperature.
It has been suggested that the presence of carbon in the deposit may
enhance corrosion. This can happen either by the transport of unburnt coal
72.0
I:I' Na.K ' C ~ COMPLEX
,,60.0 ~ "
g NaCOMPLEX "" " \ \
(,,,}
Z
36.0
0 DRY , ~
-7:
0.19
!
24.0 . . . . MoLN W \
0
850 950 1050 11N 1250
TF.MPERATURE, ~
Fig. 8. The physical state of complex alkali sulfates as a function of temperature
compared to the corrosion behavior of austenitic alloys. (After Borio, Plumley and
Sylvester42).
with the fly ash, or as the result of sooting during the oil-fired startup of a
coal-fired boiler. Rehn examined this issue, and found little effect at 675~
(1247~ however, at 790~ (1454~ carbon-free ash did not form the
alkali-iron trisulfate, and there was thus little enhanced attack due to the
synthetic ash deposit; but the carbon-containing deposit did, apparently,
produce enhanced corrosion resembling the liquid salt attack (Table II).
Further studies to identify the details of the corrosion process were not
undertaken.
Table II. Maximum Penetration in Laboratory Tests Using a Synthetic

Ash With and Without Carbon, and a Simulated Combustion Gas, at
785~ From Rehn 48
Maximum penetration (pm)
Alloy Without carbon 15% carbon added
Type 304 No attack a 457 b
Type 347 No attack Edge pitted
Type 310 No attack 305
21-6-9 No pits 254 b
IN 800H No attack 457 b
IN 811 No attack 533b
In 671 No attack --
"Ash not fused; molten alkali iron trisulfate apparently not formed.
bFused ash visible on all specimens showing attack; largely pitting.
The effect of chlorine has been a matter of some controversy for many
years. The subject was discussed in some detail in a recent Conference 5~and
further research is currently in progress to determine the effect of chlorine
in Illinois Basin coals on fireside corrosion. The experience of the CEGB
(mentioned earlier) has been that the corrosion of superheater tubes was a
linear function of coal chlorine content. However, chlorine is not detected
in the deposit, and the possible chloride species would not appear to be
thermodynamically stable at these temperatures. Holmes and Meadowcroft 5~
note that it is now believed that the hydrogen chloride (which is the form
in which all the chlorine is present in the combustion gas) acts as a release
agent for both the sodium and the potassium in the coal, although they also
speculate that perhaps there is a direct effect of chlorine after all. Cutler and
Raask 43 concluded that the deposition of alkali sulfates is not a linear func-
tion of chlorine content, but approximately 0.3% C1 is required in the coal
before rapid deposition occurs, and this has led to a criterion for coal accept-
ability if fireside corrosion is to be eliminated; however, it is almost certain
that this is an oversimplification. Rehn 48 examined the effect of adding NaC1
to his synthetic ash. At 675~ (1247~ there was perhaps some enhancement
of attack, but the effects were small. At 790~ (1454~ however, there was
evidence that the ash had fused (as was the case with carbon additions) and
there was a considerable pitting attack. However, between the pits there was
no attack at all. Mayer, Manolescu and Thorpe 52 have also studied the effect
of chlorine in a laboratory test: their approach was to add HC1 to the
synthetic combustion gas. Their gas was 80 vol% N2, 16% CO2, 4% 02,
0.2% CO, 0.18% SO2, together with 0, 0.1, 0.2, 0.8 and 2% HC1. The gas was
at 1060~ (1940~ and the metal temperatures were 560~ 700~ and
1000~ (1040, 1292, and 1832~ The exposure time was between 5 and
450 h. Sulfur prints indicated the presence of sulfide near the scale-metal
interface in specimens oxidized in the presence of HC1, which may suggest
some role in the corrosion. Brooks, quoted by Holmes and Meadowcroft ~
proposed the following expression for the rate of fireside corrosion
(C, in nm/h) for 580~176176176 and 800~
1472~ < Tg < 1400~176
C = aL([CI] - 0.1) (Tin - 500) Tg2 ( 1)
where Tm is the metal surface temperature and Tg is the gas temperature,
both in ~ [C1] is the chlorine content of the coal in wt%; a is a constant
(=4.08 • 10-13) and L = 1.0 for nonleading tubes and 2.2 for the leading
tubes, where "leading tube" means a tube in the bundle within about three
tube diameters of clear gas in front of it.
Borio, Plumley and Sylvester42 suggested a procedure for assessing the
corrosiveness of coal. Bituminous coals were obtained from six geographic
areas in the United States, and a total of eighteen 300-h tests were conducted
in the Solid Fuel Burning Test Furnace of Combustion Engineering. The

gas temperature was 1093~ (2000~ and Type 321 stainless steel was used
as the standard test material; the specimen temperature was close to 593~
(1100~ It appeared that the most significant factors were sulfur, iron, the
alkaline earths (Ca and Mg), and the alkali metals (Na and K). The correla-
tion was much better with the acid-soluble alkali than with the total alkali.
The pyritic sulfur correlated well with the iron content. Iron is present in
the coal largely as pyrite, FeS2 ; and in most U.S. bituminous coals the ratio
of pyritic and organic sulfur is fairly constant. A nomogram was constructed
from these data, and from this a corrosion index was calculated; there
appeared to be a reasonably linear correlation between this index and the
fireside corrosion experienced in the test furnace. In addition, they inserted
probes into the combustion gas stream and determined the acid soluble
Na20/K20 ratio. They noted that this value was different from that calcula-
ted on the basis of the coal analysis, but that it was probably a more accurate
measure of the corrosivity, because it would account for the different release
of the two alkalis during combustion. In their work, the effect of chlorine
was not examined, but clearly it would have an effect on the alkali release
rate.
Materials Behavior in Superheater Corrosion

There have been several tests of the relative corrosion resistance of
different alloys. Plumley, Accortt and Roczniak53 have presented a brief
report of an extensive study undertaken with U.S. Department of Energy
support to assess boiler tube alloys for advanced power cycles, using a similar
approach to that described above, coupled with longer-term field studies. In
these tests, the Appalachian coal was the least aggressive, and the Illinois
coal the most aggressive of those studied; its ash fusion temperature was
also the lowest, interestingly.
Both Kihara, Isozaki and Ohtomo, 47and Rehn q8 have used a laboratory
system to study the relative corrosion resistance of materials. Figure 9 sum-
marizes the results of Kihara et al. Sumitomo Metal Industries have also
studied the fireside corrosion of candidate boiler materials using a similar
laboratory test, and the data have been presented by Fujikawa and
Makiura54: the results generally were in agreement with Kihara et al. Alloy
17-14 CuMo, which is a high-strength steel which was used at the Eddystone
high-temperature boiler and has been considered as a candidate for advanced
steam cycle units, was considerably worse than the others. Of the more
conventional materials Type 316 stainless steel was significantly worse than
Type 304" the stabilized steels were better, with Type 347 somewhat better
than Type 321. These results suggest that Mo, and to a lesser extent Ti, had
500
400 - - /
17-14CuMo / \
Esshete 1
g 300 - -
~_200-- ~~~/.///', ~k
.m
347 ~
800H
\
Q)
9 (2-"
600 650 700 750

Temperature (~
Fig. 9. Corrosion rates of some alloys in a

laboratory test using a synthetic ash
(37.5 mole% NR2S04, 37.5 mole% K2804, 25
mole% Fe203) in a synthetic flue gas (80% N2,
15% CO2, 4% 02, 1% S Q , saturated with H20).
Exposure time 50 h. (After Kihara, Isozaki and
Ohtomo47).
adverse effects on the corrosion resistance of a Fe-18Cr-8Ni steel, whereas

Nb appeared to be beneficial. Latham, Flatley and Morris 55 have reported
the relative corrosion rates in coal-fired boilers of Types 316, 321 and 347
stainless steels, Esshete 1250, Incoloy 800; and Type 310 stainless steel and
IN 671 as claddings. Samples of Esshete 1250, Type 316 and 347, and
IN 671/IN 800 coextruded tubes were installed into leading tube positions
of the hottest reheater of a 550-MWe boiler; the metal temperature was
650~ (1202~ the gas temperature was approximately 1150~ (2102~
and the coal fired contained an average of 0.45% chlorine. After 15,400 h,
specimens were removed for examination. In addition, corrosion probe
studies were conducted for 2000 h in the same boiler, and also in a boiler
burning 0.3% C1 coal at a location where the gas temperature was 950~
(1742~ Because of its high scaling rate, the Esshete tube was bandaged
after only 6000 h to avoid failure. After completion of the test, wastage flats
were clearly visible on the Types 316 and 347 stainless steels; the IN 671-
clad tube appeared to be unattacked. Interestingly, the corrosion on the
Type 316 tube was 2.5 mm in 15,400 h, compared to 3.2 mm on the Type
347 tube, the reverse of the behavior reported by other investigators. Type
310-clad material exhibited a loss of 1.1 mm after 18,000 h in the same boiler.
The probe tests did not show a strong dependence on temperature in the
range of 600~176 (1112-1292~ with little evidence of the "bell-
shaped curve" reported in the laboratory tests (it will be remembered that
Rehn also suggested that this curve might perhaps be an artefact of the
laboratory testing procedure, and not be duplicated in practice). However,
Latham et al. suggested that perhaps the problem was that the temperatures
fluctuated over the probe, so that all sections saw a significant range of
temperatures during the exposure. Under the more aggressive conditions,
Types 316 and 347 were severely corroded, with maximum rates of more
than 100 nm/h on Type 316.
Under the less severe condition, Type 316 and Esshete 1250 were the
most heavily corroded materials. With the 0.3% C1 coal, there was intergran-
ular penetration of Type 316, Type 347, and Esshete 1250, but none on
Type 310; but with the 0.45% C1 coal there was extensive intergranular
attack; the grain boundary penetrations were sulfides. Both the Type 347
and the Type 310 formed some deep oxide-filled pits with intergranular
penetration in the metal beneath them in the higher chlorine coal environ-
ment. Overall, the authors concluded that the corrosion resistance of the
alloys was in the order IN671 (best) > Type 310>Type 347~Type
316 ~Eshete 1250. Note that it was difficult to distinguish between the last
three in spite of the lower chromium content of the Esshete 1250. If Type
310 is to be used as a cladding, it was suggested that the chromium content
be specified to be at least 25%, and that modifying it with approximately
1% Nb decreases the intergranular penetration; a minimum of 1% Si is also
beneficial.
"Bandages" formed by wrapping a strip of a corrosion-resistant mat-
erial around a corrosion-prone section of a tube have been extensively used
by the CEGB. The corrosion-resistant material is usually Sicromal.
Mortimer and Latham56 have discussed the performance of bandage shields
on Type 347 reheater tubes at the Thorpe Marsh coal-fired power station.
The lifetime of these tubes was less than four years, and several causes
were suggested: rather high operating temperatures (680~176 1256-
1292~ the occasional occurrence of a reducing atmosphere; and the use
of substantial periods of oil firing. In addition, starting before their report
(1972), a high-chlorine coal (0.3 C1) was introduced. Four bandage materials
were tried: Sicromal; a Fecralloy; an austenitic steel (Fe-22% Cr-16% Ni);
and a nickel-base alloy (Ni-16% Cr). The two latter alloys are not described
any more completely in this report. The Sicromal behaved best; the general
condition of the Fecralloy was quite good, but there was some embrittlement
and local internal oxidation and sulfidation. The remaining two alloys
exhibited more extensive attack. Bandaging depends on relatively poor ther-
mal contact between the bandage and the tube, so the bandage operates at
a higher temperature than the tube, catching the ash preferentially. As a

consequence, the heat transfer to the heat exchanger is reduced. This may
not be a problem if only small regions of the leading tubes have to be
bandaged, but for more severe corrosion extending over a greater area of
the exchanger, the reduction in heat transfer would not be acceptable. Nowa-
days, this approach is being abandoned in favor of co-extruded tubes.
Coating has been less successful: Rehn 48 has reviewed the available
information and reported on a study of a number of possible coating systems
using the test procedure described earlier. Diffusion coatings of aluminum,
chromium or silicon on various substrates were examined; the aluminized
surfaces appeared satisfactory, whereas the chromized surfaces suffered
severe local pitting; in one case, the attack was reported as being much
deeper than the uncoated substrate. In the case of siliconized materials, there
appeared to be no pitting, but the protection was not very considerable.
A variety of plasma-sprayed and metallized coatings was studied; coating
porosity was a problem. Plasma sprayed IN 671 was generally satisfactory,
although the bulk alloy showed deep local pitting. A coating consisting of
plasma sprayed MgZrO3 over an initial bond coat of Ni-AI on stainless
steel (Type 304) appeared excellent in the short-term tests. Longer-term
testing57 confirmed these good results, and indicated that the coating should
be less than approximately 300 pm to obtain good thermal cycling resistance.
In summary, it seems likely that the variations in corrosion resistance
among the conventional stainless steels are not sufficiently great to be a
reason for selecting one over another; local fluctuations in conditions may
produce larger changes than the differences observed in laboratory tests. In
severe conditions, coextruded tubes may be the most convenient solution,
in spite of the additional cost. It is necessary to optimize Type 310 if that
is to be used as a cladding, and longer-term exposures under a variety of
conditions are needed. Although some examples of rapid attack of IN 671
have been reported, it appears to be the most resistant material of those
currently available as a cladding.
MATERIALS IN COAL GASIFICATION SYSTEMS

General Features of a Coal Gasification System
The general principle of a coal gasifier for utility application is to pro-

duce a gas from coal while retaining as much of the chemical energy in the
product as possible. Gasifiers may also produce gas as a chemical feedstock,
and in some cases the desired product is methane, as a substitute natural
gas (SNG); however, in this last case there is a significant energy penalty.
Possible routes include partial oxidation, so that the product is largely car-
bon monoxide; or the water-gas reaction, in which case the product is a
mixture of carbon monoxide and hydrogen:

C 4- H20 = H2 + CO (2)
However, this reaction is endothermic, so that part of the coal must be
oxidized to carbon dioxide to provide the heat, and the product gas is a
mixture of hydrogen, carbon monoxide, carbon dioxide, and water; if the
gasifier is air-blown as opposed to oxygen blown, there will also be a consid-
erable amount of nitrogen. The relative proportions of the different gases
vary from process to process.
There are three basic ways in which the gasification reaction can be
accomplished: in a fixed bed, a fluidized bed, and an entrained gasifier:
Thefixed bed is best known as the Lurgi gasifier, which has been used
for many years. Coal is loaded into the top of the gasifier vessel, and air (or,
less commonly, oxygen) together with steam is blown in from the bottom. A
combustion zone is established at the bottom of the bed, and the hot gas rises
upward and drives the water-gas reaction (Eq. (2)). The still-hot product gas
rises through the coal bed, preheating it, first driving off the volatiles, and
at the top of the bed driving off the moisture. The incombustible coal mat-
erial (the ash) is withdrawn from the bottom of the gasifier. The product
gas is relatively cool: the exact temperature depends on the moisture and
volatile content of the feedstock. The tars and volatiles must be condensed
out, and the gas is usually water-quenched, thus also removing the ammonia
which is the product of the fuel-bound nitrogen. The sulfur in the coal is
present as H2S, and this can be removed by conventional techniques such
as the Selexol process. The problems are the losses associated with the tars
and volatiles, and the tendency for the process to blow off the coal fines at
the top of the bed without their being gasified. A high-fines feedstock is thus
undesirable.
British Gas has developed the Lurgi process to operate at higher
pressures and temperatures, so the ash actually melts and is tapped out of
the bottom. The effect is to increase the throughput. Techniques have been
developed to blow the recovered tars and the fines through the oxidant
tuyeres, increasing the overall efficiency.
Fluidized bed gasifiers use a bed of particles which is fluidized by air or
oxygen blown upwards through it. The coal is injected into the bed, which
operates so that the oxidant flow is less than the stoichiometric quantity:
partial combustion heats the bed, and the remainder of the coal is gasified.
The temperature of the bed is typicaly 850~ (1562~ and the release of
tars and volatiles is significantly reduced or eliminated. Fines are a problem
with this technology also, but proponents claim to have developed tech-
niques to overcome it. The product gas is at the bed temperature, so the
sensible heat is significant, but not really enough to warrant a heat
exchanger. The gas is normally quenched, with some recovery system for
the heat in the quench water.
The entrained gasifier resembles a burner: the coal, typically in a slurry
(although dry feed systems are available) is injected through the center of
the burner, and mixes with the oxidant which is injected in the outer con-
centric part of the burner. The temperature in the combustion zone is very
high, and all the volatiles and tars are completely gasifed. There is also no
problem with fines: in fact, the coal is typically pulverized before gasification.
The incombustible material forms a slag, which runs down the walls of the
gasifier vessel and into a quench pond at the bottom, from which it is lock-
hoppered out. The product gas temperature is very high, and it is essential
to recover the sensible heat, which is done with a radiant heat exchanger in
a vessel directly above the burner, followed by a convection heat exchanger
in an adjacent vessel.
The two principal designs of entrained gasifier are those of Texaco and
of Shell. The Texaco gasifier was the basis of the Cool Water integrated
gasifier combined cycle (IGCC) on the Southern California Edison system
which was partially funded by EPR158; the Shell gasifier is the basis of the
IGCC at Buggenum in The Netherlands. 59 Both these systems are oxygen-
blown. A major materials issue is the radiant heat exchanger (syngas cooler),
and the problem reduces to one of determining the maximum permissible
metal temperature. Much of the subsequent section is drawn from a recent
paper by Bakker. 6~
Materials for Radiant Heat Exchangers in IGCC Systems

Metal Temperatures
Most of the heat exchange surface in syngas coolers is used to evaporate
water. The metal temperature of the tubes is largely determined by the
water temperature, which depends on the desired saturated steam pressure.
Presently, the usual pressure is 10 MPa (1500 psi) which will produce 320~
(608~ saturated steam and corresponding metal temperatures of 340-
400~ (644-752~ depending on the syngas temperature. It is expected
that the steam pressure will be raised in the future to that presently used in
subcritical boilers, i.e., 18 MPa (2586 psi), producing 350~ (662~ satu-
rated steam and metal temperatures in the 380-450~ (716-842~ range.
This is the primary temperature range of interest, which most metal alloys
will experience. 6~ Some coal gasification systems will require superheating
of at least part of the steam in the syngas coolers to 500-550~ (932-
1022~ with corresponding metal temperatures in the 550-600~ (1022-
1112~ range. This is the highest temperature that alloys will experience in
present generation gasifiers, at least in significant volume; there may be
small components, such as instrumentation wells, where the temperature

may be higher, but these situations will not be discussed here.
Gas Composition
The composition of raw syngas is rarely measured before quenching
the gas after its passage through the syngas cooler. Gas compositions given
by developers are often on a water-free basis, after desulfurization. An exten-
sive compilation of gas compositions was given earlier by Natesan. 61 As an
approximation, the composition of the gas from an oxygen-blown entrained
slurry-fed gasifier like the Texaco is (in vol%) 35-45% CO, 10-15% CO2,
27-30% H2, 15-25% H20, and 0.2-1.2% H2S; for a dry-fed gasifier such as
the Shell the corresponding compositions are 62 64% CO, 2-4% CO2, 27-
30% H2, 0-3% H20, 0.2-1.2% HzS. These compositions are for the gas at
equilibrium at the gasifier operating temperature. Bakker6~ states that the
cooling is sufficiently rapid that these compositions are quenched in at the
metal temperature of the heat exchanger. This presents a problem: for ana-
lyzing a corrosion reaction in a mixed gas of this kind it is normal to describe
the gas in terms of the chemical activities of the oxidizing species, Po~, psi,
and ac. For a gas at equilibrium, these are easily calculated from the ratios
of the partial pressures of the molecular species, Pco2/pco, etc. However, it
is arguable whether it makes any sense to talk about thermodynamic activi-
ties for species in a non-equilibrium mixture, although Bakker refers to a
method proposed by Perkins. 62
It is, however, clear that the oxygen activity will be low, and much
lower in the dry-feed gas. The sulfur activity is also low, but as it turns out,
higher than the oxygen activity: it appears to be very much the same in the
two gases. In gasifier systems the carbon activity is always high, close to
unity.
Corrosion Mode
The corrosion in a gasifier environment is mixed oxidant corrosion. In
this mode, the ability of the system to form a stable protective scale is
disturbed by the second (third,...) oxidant. Generally, the only stable pro-
tective scale is an oxide, and the protective nature of the oxide scale can be
disturbed by the sulfur and/or carbon in the gas. This is the case, although
in coal gasifier environments the bulk of the reaction product is a sulfide;
the protective oxide is formed beneath this outer sulfide layer. There are
various ways that the continuity of the protective oxide scale can be dis-
turbed, and it is beyond the scope of this paper to describe them in any
detail.
The Behavior of Materials in the Gasifier Radiant Cooler

As pointed out earlier, the materials that can be used for boiler tubes
are limited by the ASME codes. For an evaporator heat exchanger, only
ferritic steels are allowable, at least for the surface in contact with water.
Generally, for the pressure and temperature conditions characteristic of a
gasifier radiant cooler, a plain carbon steel would be sufficient. However,
for such tubes, the only stable corrosion product is iron sulfide; the corrosion
rate is linear, and the rate would be unacceptable.
For high-chromium austenitic steels, the stable specie would be chrom-
ium oxide, which is capable of forming a protective scale with an acceptably
low rate of growth. The oxygen and sulfur partial pressures of most syngas
compositions fall in the Cr203 and Fe(Ni)S phase stability fields when plot-
ted on a S-O-M phase stability diagram (where M is Fe, Ni, or Cr). Within
this field there is generally a "kinetic boundary" as defined by Perkins 63 and
Natesan 61 to the right of which the growth rate of Cr203 is fast enough to
form a protective, sulfur-free, Cr203-rich scale. Unfortunately, almost all
gas compositions of commercial processes fall to the left of the kinetic boun-
dary, and form less protective mixed oxide/sulfide scales, although Cr203 is
still the thermodynamically stable species. Intuitively one would expect that
the corrosion rate would increase with decreasing Po2/ps2 ratio, although it
is not clear how the O/S ratio in the corrosion product will affect the corro-
sion rate. Isothermal corrosion tests of 600 h duration were, therefore, run
at 550~ (1022~ in a syngas to which increasing amounts of water were
added. 6~ Water additions up to 5% appeared to increase the corrosion loss
for the 20% Cr alloy, but not that of the 25% Cr alloy. All alloys showed
an abrupt decrease in corrosion rate when the water content was increased
from 10-15%, despite the fact that the change in oxygen pressure was small.
Bakker remarks that an elegant theoretical explanation for the observed
data eludes us so far.
The corrosion rates observed in syngas with higher water contents are
quite low for most alloys and lead to reasonably low corrosion losses, gen-
erally smaller than 23 nm/h (8 mil/yr) even when extrapolated linearly. The
corrosion losses in syngas with a low water content are unacceptably high
when extrapolated linearly. Consultation with various process developers
indicated that linear extrapolation is probably too conservative, and that
parabolic extrapolation is more appropriate. To check this, a few isothermal
tests of different lengths were performed in a water-free syngas. The results
indicated that this is a fair assumption for the 25% Cr alloy (Type 310), but
may not be valid for the alloys containing only 20% Cr. 6~
Aluminum and silicon are the traditional alloying additions to improve
oxidation and sulfidation resistance, presumably because they are able to
form protective silica- and alumina-rich subscales. Laboratory data at 550~

(1022~ confirmed the beneficial effect of A1 and Si on corrosion resistance
in syngas,58 although the presence of a protective oxide layer could not be
confirmed, and iron and nickel sulfides were present in the outer scale.
The performance of A1- and Si-containing alloys in actual service is less
straightforward. Diffused aluminum coatings containing 10-40% A1 on low-
alloy steels have corroded rapidly in all plants gasifying coal with a chlorine
content above 0.1-0.15%. It is believed that the HC1 in the gas removes t h e
A1 in the coating as A1CI3, which decomposes to A1203 in the scale, thus
providing additional HC1 for further attack. 64 A recent, very preliminary
corrosion test in a pressurized, dry syngas, using MA 956, suggested that
same mode of material loss may happen here in the form of pitting.
Experience with Si-containing alloys is more limited. Only one alloy
containing 3.7% Si was extensively tested in a pilot and a demonstration
plant producing syngas containing 5 25% H20. 65'66 In the more severe
environment of the pilot plant, where high-chlorine fuels were gasified, exten-
sive intergranular corrosion and cracking was noted. Under the more moder-
ate operating conditions of the demonstration plant, intergranular corrosion
occurred. Because of these experiences, the investigation of Si-containing
alloys was not continued in gasifiers producing syngas with a high water
content.
The Effect of Other Oxidants: Chlorine and Carbon

The possible effect of chlorine on coal-fired boiler waterwall corrosion,
where the local environment may not differ greatly from that in a gasifier,
has been mentioned above. Corrosion tests in pressurized syngas have
showed that HC1 may increase the corrosion rate somewhat, although the
scatter is great. So far, there is no clear-cut evidence that HC1 has an effect on
the corrosion rate of stainless steels, except for those containing aluminum.6~
The main detrimental effect of HC1 in the syngas is its effect on aqueous
corrosion during downtime. 67 Deposits on heat exchanger surfaces in plants
gasifying coals with as little as 0.1% chlorine quite often contain soluble
chlorides, such as FeC12, NaC1 and NH4C1, up to several percent. When
such deposits are allowed to get wet during downtime, the condensate can
become quite acidic, especially when some of the iron sulfide oxidizes to
iron sulfate. Polythionic acids can also form. There is ample evidence from
laboratory studies, as well as plant exposures, that rapid pitting and even
stress corrosion cracking of common stainless steels can occur under such
conditions. The best defense against downtime corrosion is the prevention
of condensates by keeping the heat exchangers above the dewpoint of the
air, or lowering the dewpoint by blanketing the syngas coolers with dry
nitrogen or air. If condensation cannot be prevented, alloys containing Mo

and V will usually resist pitting.
Carbon monoxide is the major constituent in syngas. Protective, pure
Cr203-rich scales usually do not form in syngas, so that the potential of
carburization is certainly present. Evidence for carburization in plant expo-
sure was summarized in a recent paper. 68 It was shown that carburization
readily occurs at temperatures above 600~ (1112~ in alloys such as Type
310 and Incoloy 800. Bakker 6~ commented that carburization followed by
chromium depletion and accelerated sulfidation/oxidation may be the failure
mode which will limit service life at superheater temperatures. Longer-term
exposure tests are needed to confirm this.
SUMMARY AND CONCLUDING REMARKS

The examples of components where high-temperature oxidation and
corrosion resistance are significant issues for the designer and operator that
have been instanced above are intended to show that research and develop-
ment in this general area is still needed, emphasizing the relevance of this
symposium. However, it is also intended to show that the areas of practical
importance are far from simple, and the research to optimize the corrosion
resistance must be consistent with the other requirements of the system: the
need for strength and/or toughness in the materials; the need to ensure that
the resistance to environmental degradation must be maintained throughout
the working range, and not simply at the maximum temperature; the need
to ensure that the solutions are consistent both with the manufacturability
of the component and with the integrity of the rest of the system; and that
cost is always an important consideration.
There are traps in conducting research hoping to address situations of
practical concern. Often, the lifetime required of the engineering system in
practice is very long, perhaps as long as 30 years (262,800 h). Of course, it
may be sufficient for individual components to have shorter lives: major
overhauls which would allow components to be replaced may take place at
three-year intervals (26,280 h) ; but in this case a very high degree of confi-
dence in the ability of the component to last this time will be required.
During this period, the equipment may cycle, and may even have extended
periods when it is idle. It may be difficult or inconvenient to exclude the
ambient atmosphere during these times, and the possibility of the initiation
of damage by "downtime corrosion" at low temperatures must be consid-
ered. The fuel chemistry may change for all sorts of reasons, and the corro-
sion resistance must either be tolerant of such changes, or the sensitivities
must be carefully defined. Similarly, the operating conditions may change:
a plant which was designed for steady-state operation may change to inter-
mittent operation later in its life, and again the corrosion solution must
either be tolerant, or the degree of intolerance needs to be defined.
A solution to the corrosion problem which is acceptable under labora-
tory conditions may not be acceptable at industrial scale: for example, fluc-
tuations in composition within the normal commercial specification limits
must be tolerable; the solution must be tolerant of the sort of surface finish
encountered in practice, the minor scratches that are part of real-world
installation, and so forth. Often, structures in practice are very large, and
there may be a significant amount of elastic strain in operation. For high-
temperature components, there will also be a degree of time-dependent plas-
tic strain due to creep: the solution must also be tolerant of these.
The extrapolation of short-term data is risky. Most laboratory investi-
gators will fit (often force-fit!) their results to parabolic rate curves, and use
the parabolic rate constants so determined to extrapolate to practical life-
times. First, real parabolic growth is unusual; and although the error may
not be important for short extrapolations, it can produce quite important
errors over long times. Second, in many cases the real problem is "break-
away," when the corrosion rate accelerates abruptly. To some extent, testing
may be accelerated by increasing the temperature, but this too carries consid-
erable risks. For example, below approximately 570~ (1058~ the oxide
grown on iron in oxygen or air at atmospheric pressure is principally magnet-
ite (Fe304), with a thinner outer layer of hematite (Fe203). Above this
temperature, the oxide is principally wustite, with thin outer layers of mag-
netite and hematite. Small amounts of chromium in the steel increase this
transition temperature somewhat. Reducing the partial pressure of oxygen
in the atmosphere can alter these results: in low-oxygen steam, for example,
hematite may be absent. Obviously, attempting to estimate the oxidation
behavior of low-alloy steels in boilers, which typically will experience tem-
peratures below approximately 540~ (1004~ by increasing the test tem-
perature is unlikely to be successful. In the case of Type I hot corrosion,
the initiation of the reaction depends on a number of factors which are
difficult to model with confidence, but certainly some condensed alkali sulf-
ate on the corroding surface is essential: if the temperature is raised the
sulfate may evaporate. In the case of Type II hot corrosion or molten salt-
accelerated corrosion of superheaters the problem is even more specific,
because the complex alkali-containing sulfates will dissociate if the tempera-
ture is increased significantly.
Nevertheless, it is obvious that 50,000 h testing is out of the question
on a regular basis, and certainly as a method of qualifying new materials.
Probably, 5000 h testing is required, with perhaps modest acceleration, cou-
pled with a more careful empirical determination of the form of the kinetics
for extrapolation purposes. In addition, every opportunity should be taken

to study and characterize specimens from operating units with long histories.
A further problem is that, in practice, many of the important applica-
tions involve the materials being subjected to a thermal gradient. For
example, in a boiler the heat-exchanger tubes have steam at a maximum
temperature of (say) 600~ (1112~ on the inside, and combustion gas at
a temperature of the order of 1300~ (2372~ on the outside. The metal
surface temperatures on both the inside and the outside will differ from these
fluid temperatures, and will vary with the oxide or deposit thicknesses. Some
investigators believe that the thermal flux itself may have an effect on the
corrosion.
For corrosion in mixed gases there is a further complication. The resi-
dence time of the hot gases in the vicinity of the heat exchanger or indeed
in the system itself may be quite short in comparison to the times required
for the different gas phase reactions to approach equilibrium. The metal
surface itself may catalyze some or all of these reactions, but nevertheless
the reaction will be taking place in a nonequilibrium environment. Few
investigators have considered this; and indeed the analysis is difficult and
quite different to the methods of analysis customary in the community: it
is also difficult to model in the laboratory.
In laboratory studies of oxidation, it is often assumed that the aim is
to reduce the oxidation rate by considerable amounts--two or three orders
of magnitude, for example. This is seldom the case in practice. If anything,
the rate of growth of alumina scales is too slow! If the rate of growth were
a little faster, it would be possible to extend the beneficial effects of alumina
to lower temperatures. For practical situations, an improvement in the life-
time by a factor of 3 is often not only of great value, but may be all that
can be used. There is no point in extending the life of a component beyond
the life of the rest of the system.
From these brief remarks, it can be concluded that, first, there is much
useful work to be done in the field of high-temperature oxidation and corro-
sion; and, second, the most useful research requires the abandoning of many
traditional assumptions. This is a major intellectual challenge for the next
few years.
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Current Limitations of High-Temperature Alloys in Practical Applications

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Current Limitations of High-Temperature Alloys in Practical Applications

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Oxidation of Metals, Vol. 44, Nos.

Current Limitations of High-Temperature Alloys

There are several engineering systems which require materials of construction

KEY WORDS: oxidation; corrosion; high temperatures; erosion; wear.

*Electric Power Research Institute, Palo Alto, California.

gases, or combustion gases containing sulfur, to carburizing atmospheres

The General Characteristics of the Problem

9 Cool the critical components. This may be done actively, by circulat-

In this paper, the following problems will be addressed:

9 Hot-section materials in gas turbines. This presents one of the most

Active cooling of the hot-section components

A passive cooling component, in the use of thermal barrier coatings

Hot-Section Materials in Gas Turbines

9 The directional solidification process results in large MC-type carbides

cc 100 DS MAR.M 247 \"~

(i) Single-crystal casting technology relies on the existence of a thermal

(ii) The combination of the high superheat temperatures of above

Nevertheless, it is expected that single-crystal airfoils will become a standard

engaged on a considerable in-house research effort, it is only within the last

Oxidation and Corrosion

The earliest coating was aimed at increasing the surface content of

MATERIALS IN LARGE COAL-FIRED BOILERS

of the turbine, which is called the low-pressure (LP) turbine. However,

from a fluid resembling water to a fluid resembling steam: in a glass tube

Materials Issues in Pulverized Coal Fired Boilers

Causes of Boiler Tube Failures

Waterwall Fireside Corrosion in Coal-Fired Boilers

Rapid wastage of the waterwalls is sometimes experienced in coal-fired

rates of 30 35 nm/h (10-12 mil/yr) are still occurring, compared to the

~ ~/ ~~/ / - - FeS lamellae

~,f- Fly ash spheres

However, it is clear from boiler experience that an important reaction

Fireside Corrosion of Superheaters and Reheaters

Flue gas stream

~-1~ [ Iron-rich, hard

Fig."3. Deposits and corrosion area for a. 41typical

Bishop also identified a number of factors which could contribute to

FLUE GAS DIRECTION F'LUE GAS DIRECTION

Outer Intermediate Inner

Water Soluble, % 9.0 45.4 9,0

(Na,K)3 Fe(SO4)3--which several later investigations suggested were impor-

The temperature dependence of the corrosion is usually described in

Table II. Maximum Penetration in Laboratory Tests Using a Synthetic

in the Solid Fuel Burning Test Furnace of Combustion Engineering. The

Materials Behavior in Superheater Corrosion

600 650 700 750

Fig. 9. Corrosion rates of some alloys in a

adverse effects on the corrosion resistance of a Fe-18Cr-8Ni steel, whereas

a higher temperature than the tube, catching the ash preferentially. As a

MATERIALS IN COAL GASIFICATION SYSTEMS

The general principle of a coal gasifier for utility application is to pro-

mixture of carbon monoxide and hydrogen:

Materials for Radiant Heat Exchangers in IGCC Systems

small components, such as instrumentation wells, where the temperature

The Behavior of Materials in the Gasifier Radiant Cooler

form protective silica- and alumina-rich subscales. Laboratory data at 550~

The Effect of Other Oxidants: Chlorine and Carbon

nitrogen or air. If condensation cannot be prevented, alloys containing Mo

SUMMARY AND CONCLUDING REMARKS

for extrapolation purposes. In addition, every opportunity should be taken

6. F. L. VerSnyder and R. W. Guard, Trans. A S M 52, 485 (1960).

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