BOILER TUBE GRADES

CARBON STEEL
Carbon steels show mild corrosion resistance and fair strength up to
1000F. However, their usage above 800F must take into account the
susceptibility to graphitization. Graphitization has not been a significant
problem in thicknesses encountered in boiler tubing. Use of heavy section
pipe above 800F, however, is not recommended. The application of
SA178
seamless and welded carbon steel tubing in boilers is restricted to a
maximum temperature of 800F for rimmed and 1000F for killed steel by
the ASME Boiler and Pressure Vessel Code, Section I, Power Boilers. The
Code does not list maximum allowable stresses beyond 1000F for carbon
steels.Carbon-molybdenum steels
CARBON-MOLYBDENUM STEELS
Carbon-moly steels exhibit higher creep strengths than plain carbon
steels, and are widely used in high-temperature boiler service. These
steels nominally contain 0.5% molybdenum. When exposed to
temperatures above 850-900F for long periods of time, the carbon-moly
SA209 steels are also prone to graphitization. Again, the phenomenon is sectionsize dependent, and using pipe of this grade above 850F is not
recommended. The carbide phase is not stable, and will revert to graphite.
The ASME Boiler and Pressure Vessel Code, Section I, lists allowable
stresses for carbon-moly steels up to 1000F.
INTERMEDIATE CHROME ALLOYS
This low alloy steel exhibits graphitization resistance and greater creep
strength than the carbon-moly steels. Corrosion resistance is comparable
SA213
to carbon-moly. T2 has allowable stresses listed up to 1000F in the ASME
-T2
Boiler Code.
The chromium in all of the Croloys stabilizes the carbon as chromium
carbides, thus making them immune to graphitization.
This is a 1-chromium, 1/2-molybdenum alloy which is limited to a
SA213 maximum temperature of 1200F by the ASME Boiler and Pressure Vessel
-T12 Code, Section I, Allowable Stresses. T12 is sometimes used in place of
T2 tubing because of its greater strength.
This grade has the same creep strength properties as T12. It is more
SA21 corrosion resistant than the chromium-free steels, and is fairly resistant to
3-T11 high-temperature oxidation because of its higher silicon and chromium
contents.
Oxidation resistance is important because metals exposed to elevated
temperatures for extended periods of time will accumulate a protective
coating of scale. At some minimum temperature, the scale will become
non-adherent, gradually flake, and cause solid particle erosion of turbines.

However, exfoliation rarely causes failures before creep or high

temperature yielding.
Allowable stresses are listed by the ASME Boiler and Pressure Vessel Code
to 1200F.
This 2-1/4 chromium, 1 molybdenum alloy has exceptionally high creep
SA213 properties, but is limited for applications to 1125F because of possible
-T22 higher temperature scale exfoliation. It is listed in the ASME Boiler Code
for temperatures to 1200F.
A 9-chromium-1 molybdenum alloy, T9 offers very good corrosion
resistance with good high-temperature strength. It also has good oxidation
SA213
resistance and can be used to 1200F maximum. Some times T9 is an
-T9
adequate substitute for the more expensive stainless grades. The Boiler
Code limits T9 to 1200F.
BOILER TUBE GRADES

STAINLESS STEELS Austenitic stainless steels

Austenitic stainless steels are presented in the ASME Boiler and Pressure
Vessel Code with two sets of allowable stresses. The reason for this is their
relatively low yield strength. The higher allowable stress values were
determined at temperatures where the usage would be restricted by the
short-time tensile properties.
The higher stresses exceed 62-1/2%, but do not exceed 90% of the yield
strength. At these stresses, small amounts of plastic deformation can be
expected. These higher stress values are usually used for super-heater
and reheater tubing.
The Boiler Code lists maximum allowable stresses for varying
temperatures depending on the individual austenitic stainless grade.
Variations of this 18 chromium, 8 nickel grade include 304L, 304LN, 304H
SA213
and 304N. Each of these offers excellent corrosion and oxidation
-T304
resistance along with high strength.
High strengths are maintained in the low carbon grades by controlling the
nitrogen content.
T304 has higher carbon and a minimum solution annealing temperature to
assure good long-time elevated temperature strengths. T304 grades are
limited to 1650F under oxidizing conditions. Section I of the ASME Boiler
Code lists allowable stresses up to 1500F.
T316 is similar to T304, but offers better corrosion resistance and creep
SA213 strength. The molybdenum addition to 316 increases its resistance to
-T316 pitting and crevice corrosion.
Variations of this grade include 316L, 316LN, 316H and 316N.
T321 and 347 are variations of T304 and have comparable minimum
SA213 tensile properties. These two grades are stabilized with additions of
-T321 titanium and columbian respectively, along with proper heat treatment.
and
To insure good long-time strength at elevated temperatures, T321H and
T347 347H-like 304H-were developed with higher carbon contents and specified

minimum solution annealing temperatures.

Of all the stainless steels, T309 (25 chromium, 13 nickel) and T310 (25
chromium, 20 nickel) offer the maximum resistance to oxidation and
corrosion. They also offer good high-temperature properties. Since these
steels contain ferrite, however, they are more susceptible to sigma phase.

David N. French, Sc.D

President of David N. French, Inc., Metallurgists, Northborough, MA
October 1990
Category: Design/Fabrication
Summary: The following article is a part of National Board Classic Series and it was published in the
National Board BULLETIN. (6 printed pages)

Steels are alloys of iron and carbon, usually with one or more alloying elements added to improve
some properties of the material (strength, high-temperature strength, oxidation or corrosion
resistance, for example). By definition, steels contain at least 50% iron. For welded construction, the
ASME Boiler and Pressure Vessel Code limits the carbon content to less than 0.35%. Thus, virtually
all of the materials used in the construction and repair of pressure parts of boilers fall into this
classification. Some high-temperature, corrosion-resistant alloys of nickel and chromium with less
than 50% iron are not, strictly speaking, steels, but are still occasionally used. Further, steels are
divided into two subcategories: ferritic steels and austenitic steels, depending on the arrangement of
atoms within the solid.
Steels are used in boiler construction because they are inexpensive, readily available, easily formed
and welded to the desired shape and, within the broad limits, are oxidation- and corrosion-resistant
enough to provide satisfactory service for many years. Table 1 lists the most frequently used steels,
some common tubing specifications and the maximum recommended service temperatures.

Table 1 -- Most Frequently Used Steels

ALLOY

SPECIFICATION

MAXIMUM USEFUL
TEMPERATURE

Carbon-steel

SA178, SA192,
SA210, SA106,
SA515, SA516

850o

Carbon-1/2
Molybdenum

SA209

900o

1 1/4 Chromium1/2 Molybdenum

SA213 T-11
SA335 P-11

1025o

2 1/4 Chromium1 Molybdenum

SA213 T-22
SA335 P-22

1075o

18 Chromium10 Nickel

SA213 TP304(H),
321(H), 347(H)

1500o

These five alloys cover probably 85% to 90% of the steels used of the many acceptable grades listed
in the Code. There are others that may find specific applications, for example 1/2 Chromium-1/2
Molybdenum alloy SA213 T-2, 9 Chromium-1 Molybdenum alloy SA213 T-9, and corrosion-resistant,
high-temperature alloys of nickel and chromium, SB-407.

The maximum useful temperature is determined either by corrosion or oxidation concerns that limit
the useful life before premature failure or changes within the microstructure occur that weaken the
steel too much for elevated-temperature service.
In order to understand the behavior of steels in boiler environments, a working knowledge of the
fundamentals of the metallurgy of these materials is needed. For our model we will take the alloy of
iron and carbon, historically the first steel. All matter is made up of atoms, and iron and steels are no
exception. The way these atoms arrange themselves to form a solid is referred to as a "lattice." For
convenience, assume the atoms of the metal are solid spheres in contact, similar to the stacking of
billiard balls. For steels there are two arrangements that are important. Both are cubes, but the
arrangement of the atoms within the cube differ. In one, referred to as "body-centered cubic" (BCC),
one atom is at each of the eight corners of the cube, and one atom in the center, as shown in Figure
la. The other arrangement, the "face-cantered cubic" (FCC), has one atom at the eight corners of the
cube, and one atom in the center of each of the six faces of the cube, as shown in Figure lb. The
body-cantered cubic arrangement is referred to as "ferrite," and the face-cantered cubic arrangement
is called "austenite." The addition of the element carbon does not alter this arrangement. Carbon is a
small atom and some will fit within the holes between the spheres of iron.
The amount of carbon that can fit within these FCC and BCC lattice arrangements differs. For the
body-cantered cubic arrangement of ferrite, the amount of carbon that will dissolve, (that is, fit into the
holes), is virtually nil, about 0.02%. For the face centered cubic austenite arrangement, about 2%
carbon will dissolve in the lattice holes.
To start with, in our steel model, only iron and carbon is cooled from the molten condition as, for
example during the fabrication of a steel casting or the solidification of a weld. The following changes
occur during the slow cooling:
At about 2760oF, the steel begins to solidify. The first solid that forms is a body-centered cubic "delta
ferrite." At a temperature of about 2700o F (the precise temperature depends on the exact
composition), the steel is completely solid. On further cooling, at a temperature of about 2500 degrees
F, the delta ferrite (body-centered cubic) transforms to austenite (face-centered cubic).
As an aside, all hot forming and shaping employed to make boiler tubes and piping is done in the
austenite temperature range of 1650oF to 2000oF. With the continued cooling, the face-cantered-cubic
austenite begins to transform to body-centered-cubic ferrite at a temperature of around 1600 oF, and
again, the exact temperature depends on the composition. Continuous cooling to 1340 oF changes the
relative amounts of ferrite and austenite until at 1340o F, the remaining austenite transforms to
pearlite. The pearlite is a mixture of ferrite and a carbon-rich constituent called "iron carbide" or
"cementite." The ferrite is nearly pure iron, dissolving less than 0.02% carbon. The iron carbide has a
lattice arrangement that is referred to as "hexagonal" and is more complex than the simple cubic
arrangements shown in Figures 1a and 1b. The relative amounts of ferrite and iron carbide will differ
depending on the amount of carbon within the alloy; higher carbon grades will have more pearlite than
lower carbon grades.
The transformation from austenite to ferrite and iron carbide requires an un-mixing of the carbon. The
carbon completely dissolves in austenite, and virtually none dissolves in ferrite. When the cooling is
slow enough, this separation of dissolved carbon in austenite to a separate constituent, iron carbide,
occurs in an orderly way, and pearlite forms. Pearlite is a sandwich of alternating layers of ferrite and
iron carbide. When cooling rates are too rapid, there is no time for the formation of iron carbide and
pearlite. The carbon is trapped in the austenite, which is unstable at low temperatures. Rapidly cooled
austenite does change its atomic arrangement to martensite, a hard, brittle material with a lattice that
is a distorted cube, called "body-cantered tetragonal." This transformation can be an important
concern during welding and can lead to underbead cracking.
Ferritic steels are "ferrite" and iron carbide (pearlite) at room temperature. Other than carbon, the
principal alloying elements are chromium and/or molybdenum; T-l, T-ll, and T-22 are the common
examples. When sufficient chromium and nickel (18% Cr and 8% Ni) are added, the FCC "austenite"
lattice remains stable to room temperature; hence this class of steels is called "austenitic." Since
these 18-8 chromium-nickel alloys have excellent corrosion resistance and do not show rust-colored
corrosion products, they are referred to as "stainless" steels. The nickel-chromium alloys with less
than 50% iron (for example, SB 407) are also austenitic, as their lattice arrangement is FCC as well.

Atoms of iron are quite small, about 100,000,000 would fit in an inch. Thus, useful sizes of material
contain a huge number of individual atoms.
The next step in the building block of making useful shapes is a crystal or grain. All of the atoms
arranged within a given lattice in the same orientation defines a crystal. The grain size is variable, but
within steels is fairly small; about 1,000 to the inch or about 1 mil (0.001") in diameter, for example.
Thus there are about 100,000 atoms of iron across and perhaps 1015 atoms (10 followed by 15
zeros) in an individual crystal.
Since crystals are small, another large number is needed to make a useful shape. Neighboring
crystals or grains do not have the same orientation of the lattice. Where two grains come together and
meet, they form a crystal or grain boundary. The lattice arrangement in these two crystals is the same,
but the orientation is different. A grain may be characterized by long-range order in the atomic
arrangement. At the grain boundary, individual atoms are not arranged regularly and therefore shortrange disorder characterizes the grain boundaries.
The observation and interpretation of grain structure is called metallography; and, as shall be evident
later, the appearance under the microscope can tell a great deal about the past history of a piece of
steel. Grain boundaries will play important roles in the interpretation of some failures, and these
features will be more fully covered then. The region of short-range atomic disorder is more easily
corroded because of the imperfect bonding of neighboring atoms within the confusion of the grain
boundary. A more rapid corrosion of these grain boundaries allows the crystal structure to be
examined. A controlled corrosion, called "etching", of a smoothly polished surface attacks the
disorganized grain boundaries more rapidly than it does the well-organized crystals themselves.
When examined at a high magnification in a microscope, the light reflects off the crystals like a mirror,
but is trapped within the groove of a grain boundary; and thus the grain boundary shows up as a black
line within the field of view.
The addition of other metals to iron improves the strength. There are two kinds of alloying elements,
substitutional and interstitial. When the metallic atoms are similar in size to iron, for example
chromium, nickel, molybdenum, manganese, and silicon, the atoms can substitute for iron at
individual lattice points, and are called "substitutional solid solutions." When small atoms are used, for
example carbon, nitrogen, or boron, the small atoms (relative to the size of the iron atom), fill the
holes within the lattice and are called "interstitial solid solutions." Carbon is by far the most common
alloying element and has importance all out of proportion to its content. For example, 0.2% carbon will
increase the strength of pure iron from about 40,000 psi to about 60,000 psi. To get the same 50%
improvement in strength takes more than 2 1/ 2% chromium and 1% molybdenum, as a comparison
of the strength of SA192 and SA213 T-22 will indicate.
This article has introduced the concepts of atomic arrangement or lattice, crystals or grains, and grain
boundaries and metallography.
Metallurgical Failures in Fossil Fired Boilers , John Wiley & Sons, Inc., N.Y., N.Y. 1983.

Editor's note: The previous article is reprinted from the October 1990 National Board BULLETIN.
Some ASME Boiler and Pressure Vessel Code requirements may have changed because of
advances in material technology and/or actual experience. The reader is cautioned to refer to the
latest edition and addenda of the ASME Boiler and Pressure Vessel Code for current requirements.
Users may request favorite "classic" BULLETIN articles or General Meeting presentations by sending
the article title/subject information via email. For more information, please Contact Us.

Comparing materials for high-temperature

steam piping

The use of X20 and P91 in power

stations
TPJ - THE TUBE & PIPE JOURNAL OCTOBER/NOVEMBER 2002
JANUARY 16, 2003

By: P.K. Saha

Of all the materials used for high-temperature steam piping,

X20 (12 percent chromium, 1 percent molybdenum, 1/4 percent
vanadium) and P91 (9 percent chromium, 1 percent
molybdenum, 1/4 percent vanadium) stand out because of their
very high creep rupture properties, even at elevated

temperatures.
X20 was introduced in the 1950s in Germany and used in steam lines operating at temperatures
of 530 degrees C and higher for fossil fuel-fired power generating sets of 150 megawatts and
more. However, two factors limited its use: the extreme care needed for its fabrication and
welding and its noninclusion in the American Society of Mechanical Engineers (ASME) Code
B31.1.
P91, introduced in the 1980s in the U.S., has both very high strength at elevated temperatures
and good fabrication properties. These features have made P91 the material of choice for hightemperature steam and other, similar noncorrosive services.

X20 Material
X20 material was first used in India for high-temperature steam piping around 1970. The next
application in India took place nearly two decades later, when the Tata Electric Co.
(www.tata.com) selected the material for both the main steam and hot reheat lines of its Trombay
power station's 500-MW units.
The use of X20 in preference to P22 (2-1/4 percent chromium, 1 percent molybdenum) in the
latter application allowed wall thickness reductions of about 50 percent. These reductions

resulted in easier handling; less energy needed for preheating, welding, and postweld heat
treatment; and faster start-up, load changes, and shutdown of the unit.
Overall savings in the cost of the piping supplies and their fabrication, including welding, was
claimed to be about 40 percent.1
Trombay Unit 6 became operational in 1989. Since then X20 has been used in India for main
steam piping in six other power stations.
By the time P91 was included in the ASTM specification A335 in 1984, more than 100,000 metric
tons of X20 tube and pipe had been used in power stations worldwide. The cumulative operating
time with the material steel had been more than 4 million hours.2Operating behavior in more than
300 high-capacity power stations has been excellent,3and failures have been limited to a few
instances occurring when it was introduced because of lack of knowledge about the material's
properties.4
Its creep rupture properties have been well-established through laboratory tests and more than
200,000 hours of operation.5
In spite of such strong credentials, X20 has not been included in the ASME Boiler & Pressure
Vessel Code. This is likely one of the main reasons that the U.S. remains a notable exception in
the long list of countries using this material.

Figure 1
When properly heat-treated, P22, X20, and P91 achieve
these tensile properties at room temperature.

P91 Material
The U.S. had been trying to develop a new material since the middle 1970s to bridge the gap
between ferritic P22 and austenitic steels with respect to creep rupture strength for hightemperature service from 540 to 600 degrees C. Development of any new material, especially for
high-temperature service, requires many years, because creep rupture strengths are established
based on longtime exposure to a range of intended service temperatures.
As a result of these developmental efforts, a new material, designated P91, was introduced in the
U.S. in the 1980s by Oak Ridge National Laboratory (ORNL, www.ornl.gov), assisted by
Combustion Engineering. This material has proven to have such good strength and fabrication
properties that the use of X20 has practically been discontinued in Europe. In fact, even
renovations of old power plants are being made with P91 material for steam circuits operating in
the creep range.

P91 is a modified form of P9 (9 percent chromium, 1 percent molybdenum) steel. The steel can
have low impurity limits, thanks to the development of processes such as argon-oxygen
decarburization (AOD) and electroslag remelting (ESR), which make the steel behave
consistently during fabrication and resist the effects of aging. When properly heat-treated as
specified in ASTM specification A335, the steel acquires room temperature properties as shown
in Figure 1.
The steel has high creep rupture strength because of the precipitation of submicroscopic
vanadium and niobium carbonitrides. Low carbon content aids its fabrication characteristics. The
material responds well to hot and cold bending, as well as to welding.

Comparison of X20 and P91

Figure 2
P91 (top) and X20 (bottom) both are martensitic steels
with similar transformation behavior.
P91 and X20 both are martensitic steels with similar transformation behavior (see Figure 2).
Martensite formation temperature for P91 is about 400 degrees C. Welding of P91 steel is,
therefore, carried out below this temperature using preheat and interpass temperatures in the
range of 200 to 300 degrees C.
The maximum hardness in the weld metal and heat-affected zone in as-welded condition is about
450 HV10, which is lower than that of X20 (greater than 500 HV10). Heavier-wall P91
components may be cooled to room temperature after welding. The joint should, however, be
kept dry after welding until postweld heat treatment is complete to avoid stress-corrosion cracking
caused by the presence of humidity.6
Martensite formation temperature for X20 is about 300 degrees C, so welding may be carried out
either at 250 degrees C (just below the martensite formation temperature) or in the
nontransformation range beyond 400 degrees C. The higher temperature helps prevent high

hardness values and the attendant risk of cracking during welding. In any case, except for very
thin-wall components, X-20 weld deposit must be cooled down to about 100 degrees C and held
there for at least one hour for the transformation of austenite into martensite to be complete. The

Figure 3
Several brands of welding consumables can be used with P22 and P91, while only one brand is
recommended for use with X20.
component then is subjected to a tempering treatment at between 730 and 760 degrees C for at
least two hours.7
Typical welding consumables recommended for P22, X20, and P91 are shown in Figure 3, and
typical nondestructive testing practices recommended for P91 are shown in Figure 4.
Following are some considerations that influence a choice between P91 and X20:
1.

Allowable stress, per ASME B31.1 code, is the same for both P91 and X20 at 540
degrees C. The allowable stress is increasingly higher for P91 at higher temperatures.
Therefore, any advantages of X20 based on its lower thickness requirement can be obtained
by using P91 at 540 degrees C and higher.

2.

Use of X20 demands extreme care in fabrication and welding of the piping components.
Important parameters include induction heating of thicker weld joints; special cooling and
storage of bends before heat treatment; low-speed grinding performed intermittently to
prevent overheating and cracking; completion of welding and heat treating in one cycle; and
extensive NDT for weld joints.

3.

The thermal expansion coefficient of P91 is comparable to that of X20.

4.

The thermal conductivity of P91 is higher than that of X20.

5.

P91 can be readily machined with cutting tools similar to those used for X20.

6.

P91 has a lower chromium content, which helps to conserve material.

Figure 4
Several types of nondestructive testing
typically are recommended for P91.
Confidence in the use of P91 steel has grown substantially since its first use. ASTM approved the
steel under designation A213 Gr. T91 in 1983 and A335 Gr. P91 in 1984. Inclusion of P91 plates,
forgings, flanges, and fittings in ASTM standards, and commercial manufacture of such
components to these standards, continues to evolve.

A Promising Future
At temperatures higher than 540 degrees C, P91 has increasingly higher allowable stress than
X20. It now is possible for fossil fuel-fired power stations to achieve higher pressure and
temperature parameters on main steam piping, and thereby realize higher thermal efficiency,
using this material. This saves recurring fuel costs and also reduces pollutants, because less fuel
is burned.
P91/T91 may be used to replace sections of boiler header and pressure parts that occasionally
reach temperatures higher than permissible design limits for P22 or other low-alloy chromiummolybdenum-vanadium steels. T91 also is being applied in superheater and reheater circuits,
which used to require austenitic steel because of the design temperatures.
P91 also has been used recently in petrochemical plants for cracking and hydrotreating furnaces
that employ higher operating temperatures to increase the yield of unleaded, high-octane fuels.
P91 has a promising future, and its applications are sure to increase until another new material is
in a position to challenge it.
P.K. Saha is head of quality and management representative for Bharat Heavy Electricals Limited
(BHEL) Power Sector -- Eastern Region, Gillander House, Block B & C, 4th Floor, 8, N.S. Road,
Kolkata-700001, India. BHEL is an engineering and manufacturing organization engaged
primarily in design, manufacture, supply, installation, and servicing of power plant and industrial
equipment.
Reprinted with permission from BHEL Journal, Volume 20, No. 1, March 1999.

Notes
1. V.L. Gopalakrishnan, Welding of X20 Pipes for Conveyance of High Pressure Steam for 500
MW Power Plant -- an Indian Experience (The Tata Power Co. Ltd., 1991), pp. 377-383.
2. G. Kalwa, State of the Development and Application Techniques of the Steel X20CrMoV121
(Mannesmann).

3. W. Bendick, V. Harrmann, and M. Zschau, Retrofitting of Exhausted Steamline Components

(Mannesmann).
4. K. Niederhoff, G. Wellnitz, M. Zschau, and D. Ziessnitz, Properties and Fabricability of Creep
Resistant 9-12% Cr Steels for High Pressure Piping System in Power Plants (Mannesmann,
1991), pp. 221-262.
5. Ibid.
6. Ibid.
7. F. Bruhl and H. Musch, Welding of Alloyed Ferritic and Martensitic Steels in Piping Systems for
High Temperature Service (Mannesmann).