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Chapter 7
Metallurgy, Materials and
Mechanical Properties
Boilers, pressure vessels and their associated components are primarily made of metals. Most of these
are various types of steels. Less common, but still important, are cast irons and nickel base alloys. Finally,
ceramics and refractories, coatings, and engineered
combinations are used in special applications.
Metallurgy
Crystal structure
The smallest unit of a metal is its atom. In solid
structures, the atoms of metals follow an orderly arrangement, called a lattice. An example of a simple
point lattice is shown in Fig. 1a and the unit cell is
emphasized. The lengths of the unit cell axes are defined by a, b and c, and the angles between them are
defined by , and in Fig. 1b. The steels used in
boilers and pressure vessels are mainly limited to two
different lattice types: body-centered cubic (BCC) and
face-centered cubic (FCC). (See Fig. 2.) Where changes
in the structure or interruptions occur within a crystal, these are referred to as defects. Crystal (or grain)
boundaries are a type of crystal defect. A few useful
structures are composed of a single crystal in which
all the unit cells have the same relationship to one
another and have few defects. Some high performance
jet engine turbine blades have been made of single
crystals. These structures are difficult to make, but are
worthwhile; their strength is very high as it is determined by close interactions of the atomic bonds in their
optimum arrangement. The behavior of all other metallic structures, which make up the huge majority of
engineering metallic materials, is determined by the
nature and extent of the defects in their structures.
Structures are made of imperfect assemblies of imperfect crystals, and their strengths are orders of magnitude lower than the theoretical strengths of perfect
single crystals.
Defects in crystals
Perfect crystals do not exist in nature. The imperfections found in metal crystals and their interactions
control their material properties.
Point defects Point defects include missing atoms
(vacancies), atoms of a different element occurring on
crystal lattice points (substitutionals), and atoms of a
different element occurring in the spaces between
crystal lattice points (interstitials). Thermally created
vacancies are always present, because they reduce the
free energy of the crystal structure by raising its entropy. There is an equilibrium number of vacancies
present; this number varies with the temperature of the
crystal. The presence of such vacancies permits diffusion (the transport of one species of metal atom through
the lattice of another) and helps facilitate some forms
of time dependent deformation, such as creep.
Vacancies can also be created by irradiation damage and plastic deformations, and the thermodynamically controlled processes of diffusion and creep can
also be affected by these other processes.
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7-2
7-3
7-4
7-5
Fig. 9 General effect of carbon on the mechanical properties of hotrolled carbon steel.
7-6
7-7
(316C). A full anneal refines grain structure and provides a relatively soft, ductile material that is free of
internal stresses.
Solution annealing is done by heating an austenitic stainless steel to a temperature that puts most of
the carbides into solution. The steel is held at this temperature long enough to achieve grain growth. It is
then quenched in water or another liquid for fast cooling, which prevents most of the carbides from
reprecipitating. This process achieves optimum creep
strength and corrosion resistance. For many boiler
applications, austenitic stainless steels require the high
creep strength of a coarse grain structure but do not
require aqueous corrosion resistance, because they are
only exposed to dry steam and flue gases. Solution
treatment, used to achieve grain growth, is required for these
applications, but the quenching step is not required.
Stabilization annealing is performed on austenitic
stainless steels used in severe aqueous corrosion environments. The steel is first solution annealed, then
reheated to about 1600F (871C) and held there. Initially, chromium carbides precipitate at the grain
boundaries in the steel. Because these are mostly of
the complex M23C6 type, which are very high in Cr, the
austenite adjacent to the grain boundaries is depleted
of chromium. This would normally leave the steel susceptible to corrosive attack, but holding it at 1600F (871C)
permits the Cr remaining in the austenite solution to redistribute within the grains, restoring corrosion resistance, even adjacent to the grain boundaries.
Intercritical annealing and isothermal annealing
are similar. They involve heating a hypoeutectoid ferritic steel above the lower critical transformation temperature (A1 in Fig. 5) but below the upper critical
temperature, A3. This dissolves all the iron carbides but
does not transform all the ferrite to austenite. Cooling slowly from this temperature through A1 produces
a structure of ferrite and pearlite that is free of internal stresses. In intercritical annealing, the steel continues to cool slowly in the furnace, similarly to full
annealing. In isothermal annealing, cooling is stopped
just below A1, assuring complete transformation to
ferrite and pearlite, and eliminating the potential for
bainite formation.
Process annealing, sometimes called subcritical annealing or stress relieving, is performed at temperatures just below the lower critical temperature A1, usually between 950 and 1300F (510 and 704C). Process
annealing neither refines grains nor redissolves cementite, but it improves the ductility and decreases
residual stresses in work hardened steel.
Normalizing is a variation of full annealing. Once
it has been heated above the upper critical temperature, normalized steel is cooled in air rather than in a
controlled furnace atmosphere. Normalizing is sometimes used as a homogenization procedure; it assures
that any prior fabrication or heat treatment history
of the material is eliminated. Normalizing relieves the
internal stresses caused by previous working and, while
it produces sufficient softness and ductility for many purposes, it leaves the steel harder and with higher tensile
strength than full annealing. To remove cooling stresses,
normalizing is often followed by tempering.
Fabrication processes
Any mechanical work applied to the metal below its
recrystallization temperature is cold work. Mechanical work performed above the recrystallization temperature is hot work and the simultaneous annealing
that occurs at that temperature retards work-hardening. The recrystallization temperature is dependent on
the amount of deformation. If a material is formed at a
temperature significantly above room temperature, but
below its recrystallization temperature, the process is
sometimes referred to as warm working.
The temperature at which steel is mechanically
worked has a profound effect on its properties. Cold
work increases the hardness, tensile strength and yield
strength of steel, but its indices of ductility elongation and reduction of area are decreased. The extent of the work-hardening, with progressive elongation of the grains in the direction of working, depends
on the amount of cold work and on the material. If
the work-hardening caused by the necessary shaping
operation becomes excessive, the ductility may be exhausted and further work can cause fracture.
Hot working variations include forging, rolling,
pressing, extruding, piercing, upsetting and bending.
Most of these are largely compressive operations, in
which the metal is squeezed into a desired shape. They
Steam 41 / Metallurgy, Materials and Mechanical Properties
7-9
Welding
Joining of boiler pressure parts and of nonpressure
parts to pressure parts is almost always accomplished
by welding. This is particularly true of high temperature, high pressure boilers, whose service conditions
are too severe for most mechanical joints (bolted
flanges with gaskets) and brazed joints.
Welding Processes
Fusion
Energy
Beam
Gas
Welding
Electron
Beam
Oxyacetylene
Brazing
Shielded Metal
Arc
Pressure
Thermit
Process
Arc
Welding
Smith
Friction
Cold
Resistance
Welding
Butt
Flash
Laser
Beam
Metallic
Arc
Flux Cored
Arc
Gas
Shielded
Submerged
Arc
Gas Metal
Arc
Electroslag
Spot
Seam
Gas Tungsten
Arc
7-10
7-11
Materials
Almost all of the materials used in constructing
boilers and pressure vessels are steels and the vast
majority of components are made of carbon steels.
Carbon steels are used for most types of pressure and
nonpressure parts: drums, headers, piping, tubes,
structural steel, flues and ducts, and lagging.
Carbon steels may be defined by the amount of carbon retained in the steel or by the steelmaking practice. These steels are commonly divided into four
classes by carbon content: low carbon, 0.15% C maximum; medium-low carbon, between 0.15 and 0.23%
C; medium-high carbon, between 0.23 and 0.44% C;
and high carbon, more than 0.44% C. However, from
a design viewpoint, high carbon steels are those over
0.35%, because these can not be used as welded pressure parts. Low carbon steels see extensive use as pressure parts, particularly in low pressure applications
where strength is not a significant design issue. For
most structural applications and the majority of pressure parts, medium carbon steels, with carbon contents
between 0.20 and 0.35%, predominate.
Carbon steels are also referred to as killed, semikilled, rimmed and capped, depending on how the
carbon-oxygen reaction of the steel refining process
was treated. During the steelmaking process, oxygen,
introduced to refine the steel, combines with carbon
to form carbon monoxide or carbon dioxide, and also
exists as excess oxygen. If the oxygen introduced is
not removed or combined prior to or during casting by
the addition of Si, Al, or some other deoxidizing agent,
the gaseous products are trapped during solidification
of the metal in the mold. The amount of gas evolved
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7-13
7-14
7-15
Mechanical properties
Low temperature properties
Steels of different properties are used in boilers,
each selected for one or more specific purposes. Each
steel must have properties for both manufacturing and
satisfactory service life. Each particular type, or grade,
of steel must be consistent in its properties, and tests
are normally run on each lot to demonstrate that the
desired properties have been achieved.
Specifications standardizing all the conditions relating to test specimens, methods and test frequency
have been formulated by the American Society for
Testing and Materials (ASTM) and other authorities.
7-16
Tensile test
In the tensile test, a gradually applied unidirectional pull determines the maximum load that a material can sustain before breaking. The relationship
between the stress (load per unit area) and the corresponding strain (change of length as a percent of the
original length) in the test piece is illustrated in the
stress-strain diagrams of Figs. 15 and 16. The metal
begins to stretch as soon as the load is applied and, for
some range of increasing load, the strain is proportional
to the stress. This is the elastic region of the stress-strain
curve, in which the material very closely follows Hookes
Law: strain, , is proportional to stress, . The proportionality constant may be considered as a spring constant and is called Youngs modulus, E. Youngs modulus is a true material property, characteristic of each
alloy. Youngs modulus for steel is approximately 30
106 psi (206.8 106 kPa) at room temperature.
If the stress is released at any point in this region,
the test specimen will return to very nearly its initial
dimensions. However, if the stress is increased beyond
a certain point, the metal will no longer behave elastically; it will have a permanent (plastic) elongation,
and the linear relationship between stress and strain
ceases. This value is known as the proportional limit
of the material and, in this discussion, may be considered practically the same as the elastic limit, which
may be defined as the maximum stress that can be
developed just before permanent elongation occurs.
Hardness test
Hardness may be defined as resistance to indentation under static or dynamic loads and also as resistance to scratching, abrasion, cutting or drilling. To
the metallurgist, hardness is important as an indicator of the effect of heat treatment, fabrication processes, or service exposure. Hardness values are
roughly indicative of the ultimate tensile strength of
steels. Hardness tests are also used as easy acceptance
tests and to explore local variations in properties.
Steam 41 / Metallurgy, Materials and Mechanical Properties
Toughness tests
Toughness is a property that represents the ability
of a material to absorb local stresses by plastic deformation and thereby redistribute the stresses over a
larger volume of material, before the material fails
locally. It is therefore dependent on the rate of application of the load and the degree of concentration of
the local stresses. In most steels, it is also temperature
dependent, increasing with increasing temperature
(although not linearly). Toughness tests are of two
types, relative and absolute.
Notched bar impact tests are an example of the relative type. The most common is the Charpy test, in
which a simple horizontal beam, supported at both
ends, is struck in the center, opposite a V-shaped notch,
by a single blow of a swinging pendulum. A Charpy
specimen is illustrated in Fig. 17a. The energy absorbed by the breaking specimen can be read directly
on a calibrated scale and is expressed in ft lb units.
The specimen is also examined to determine how
much it has spread laterally and how much of its fracture surface deformed in shear versus cleavage. The
toughness is expressed in units of absorbed energy (ft
lb or J), mils (thousandths of an inch or mm) lateral
expansion and percent shear. The values are characteristic of not only the material and temperature, but
also of the specimen size. Therefore, comparison between materials and tests have meaning only when
specimen geometries and other test conditions are identical. Specimens are inexpensive and the test is easy
to do. Often, vessel designers are interested in the
variation of toughness with temperature. Fig. 18 illustrates the variation in toughness with temperature
of 22 heats of a fine grained carbon steel, SA-299, as
determined by Charpy testing. This material displays
a gradual transition from higher to lower toughness.
Another toughness test, and one that provides a
more sharply defined transition, is the drop-weight
test. The specimen for this test is shown in Fig. 17b. A
known weight is dropped from a fixed height and impacts the specimen. This is a pass or fail test and is
performed on a series of specimens at varying temperatures, selected to bracket the break versus nobreak temperature within 10F (6C). If the impact
causes a crack to propagate to either edge of the specimen from the crack-starter notch in the brittle weld
bead deposited on the face of the specimen, the specimen is considered to have broken at that temperature.
The lowest temperature at which a specimen fails
determines the nil-ductility transition temperature
7-17
Formability tests
Several different types of deformation tests are used
to determine the potential behavior of a material in fabrication. These include bending, flattening, flaring and
cupping tests. They furnish visual evidence of the capability of the material to withstand various forming operations. They are only a rough guide and are no substitute for full scale testing on production machinery.
7-18
the increase in strength over that at room temperature of carbon and many low alloy steels (with corresponding decrease in ductility) over the temperature
range of 100 to 600F (38 to 316C). As the temperature is increased beyond 600 to 750F (316 to 399C),
the strength of the carbon and most of the low alloy
steels falls off from that at room temperature with a
corresponding increase in ductility.
7-19
Specification
SA-178A
SA-192
SA-178C
SA-210A1
SA-106B
SA-178D
SA-210C
SA-106C
SA-216WCB
SA-105
SA-181-70
SA-266Cl2
SA-516-70
SA-266Cl3
SA-299
SA-250T1a
SA-209T1a
SA-250T2
SA-213T2
SA-250T12
SA-213T12
SA-335P12
SA-250T11
SA-213T11
SA-335P11
SA-217WC6
SA-250T22
SA-213T22
SA-213T23
SA-335P22
SA-217WC9
SA-182F22Cl1
SA-336F22Cl1
SA-213T91
SA-335P91
SA-217C12A
SA-182F91
SA-336F91
SA-213T92
SA-213TP304H
SA-213TP347H
SA-213TP310H
SB-407-800H
SB-423-825
Nominal
Composition
C-Steel
C-Steel
C-Steel
C-Steel
C-Steel
C-Steel
C-Steel
C-Steel
C-Steel
C-Steel
C-Steel
C-Steel
C-Steel
C-Steel
C-Steel
C-Mo
C-Mo
1/2Cr-1/2Mo
1/2Cr-1/2Mo
1Cr-1/2Mo
1Cr-1/2Mo
1/2Cr-1/2Mo
1-1/4Cr-1/2Mo-Si
1-1/4Cr-1/2Mo-Si
1-1/4Cr-1/2Mo-Si
1-1/4Cr-1/2Mo
2-1/4Cr-1Mo
2-1/4Cr-1Mo
2-1/4Cr-W-V
2-1/4Cr-1Mo
2-1/4Cr-1Mo
2-1/4Cr-1Mo
2-1/4Cr-1Mo
9Cr-1Mo-V
9Cr-1Mo-V
9Cr-1Mo-V
9Cr-1Mo-V
9Cr-1Mo-V
9Cr-2W
18Cr-8Ni
18Cr-10Ni-Cb
25Cr-20Ni
Ni-Cr-Fe
Ni-Fe-Cr-Mo-Cu
Product
Form
ERW tube
Seamless tube
ERW tube
Seamless tube
Seamless pipe
ERW tube
Seamless tube
Seamless pipe
Casting
Forging
Forging
Forging
Plate
Forging
Plate
ERW tube
Seamless tube
ERW tube
Seamless tube
ERW tube
Seamless tube
Seamless pipe
ERW tube
Seamless tube
Seamless pipe
Casting
ERW tube
Seamless tube
Seamless tube
Seamless pipe
Casting
Forging
Forging
Seamless tube
Seamless pipe
Casting
Forging
Forging
Seamless tube
Seamless tube
Seamless tube
Seamless tube
Seamless tube
Seamless tube
Min
Tensile,
ksi
(47.0) (26.0)
(47.0) (26.0)
60.0
37.0
60.0
37.0
60.0
35.0
70.0
40.0
70.0
40.0
70.0
40.0
70.0
36.0
70.0
36.0
70.0
36.0
70.0
36.0
70.0
38.0
75.0
37.5
75.0
40.0
60.0
32.0
60.0
32.0
60.0
30.0
60.0
30.0
60.0
32.0
60.0
32.0
60.0
32.0
60.0
30.0
60.0
30.0
60.0
30.0
70.0
40.0
60.0
30.0
60.0
30.0
74.0
58.0
60.0
30.0
70.0
40.0
60.0
30.0
60.0
30.0
85.0
60.0
85.0
60.0
85.0
60.0
85.0
60.0
85.0
60.0
90.0
64.0
75.0
30.0
75.0
30.0
75.0
30.0
65.0
25.0
85.0
35.0
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
950
950
950
950
950
950
950
950
950
950
950
800
800
800
800
975
975
1025
1025
1050
1050
1050
1050
1050
1050
1100
1115
1115
1115
1100
1115
1115
1100
1150
1150
1200
1150
1150
1200
1400
1400
1500
1500
1000
1,2
1
2
3
2
3
3
3
4,5
4
6
6
5
5
Notes:
1. Values in parentheses are not required minimums, but are expected minimums.
2. Requires special inspection if used at 100% efficiency above 850F.
3. Limited to 800F maximum for piping 10.75 in. OD and larger and outside the boiler setting.
4. Limited to 875F maximum for applications outside the boiler setting.
5. Requires special inspection if used at 100% efficiency.
6. Maximum OD temperature is 1025F. Maximum mean metal temperature for Code calculations is l000F.
to enhance creep strength. A new family of Ni and NiCr-Co alloys is also available, specifically for advanced
supercritical and advanced supercritical boiler designs.
Fuel ash corrosion considerations might dictate the
use of higher alloys at lower temperatures. This is
common in process recovery and refuse-fired boilers
with very corrosive flue gas and ash. For example, SB407-825 (42Ni-21.5Cr-3Mo-2.25Cu-0.9Ti-bal Fe) is
used in the highly corrosive regions of refuse boiler
superheaters, even at temperatures below 1000F
(538C). In extreme cases, bimetallic tubes, with a core
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of a Code material for pressure retention and a cladding of a corrosion resistant alloy, are used for both
furnace wall and superheater applications. Some common combinations are SA-210A1/304L, SA-210A1/
Alloy 825, and SB-407-800H/50Cr-50Ni.
Selection factors
Many factors influence material selection in a superheater. These include cost as well as performance
factors (heat transfer surface area required, final
steam temperature, total mass flow through the tubes,
Steam 41 / Metallurgy, Materials and Mechanical Properties
Cost
Material cost is usually the single largest factor
affecting material selection when more than one material candidate exists for a given set of boiler application conditions. Raw material cost is established by
taking into account each materials allowable design
stress, at design temperature and pressure, and required mass flow requirements for the water or steam.
Pressure part sizes are established, average weight
determined, and material cost is estimated when
knowing the raw material cost offered by the selected
raw material supplier. Other factors are also considered such as required corrosion allowance, if any, and
unique manufacturing costs and risks. Once this
evaluation is accomplished and comparison of materials
is completed, it is quite common to find that stronger,
higher alloys become economically attractive over lower
strength, less costly steels at operating conditions usually acceptable and appropriate for the lower alloy steel.
Drums
Carbon steel plate is the primary material used in
drums. SA-299, a 75,000 psi (517.1 MPa) tensile
strength material, ordered to fine grain melting practice for improved toughness, is used for heavy section
Fig. 25 The 9Cr-1Mo-V superheater outlet header features high strength and thin material less susceptible to creep-fatigue failure.
7-23
stream and on the characteristics of the fuel. Temperatures to which these metal parts are exposed may
range from 1000 to 2800F (538 to 1538C). Welding of
such austenitic castings to ferritic alloy tubes presents
a dissimilar metal weld that is susceptible to failure.
Normal practice is to use a nickel-base filler metal that
better matches the thermal expansion properties of the
ferritic tube than would an austenitic stainless weld
composition. If possible, a ferritic alloy weld rod should
be used to further reduce stresses against the ferritic
pressure part, provided there is adequate weldability
and operating conditions at the weld location are acceptable. Special patented nonwelded constructions
are also used where such combinations are required.
Life may be shortened if these steels are exposed to
flue gases from fuel oil containing vanadium compounds. Sulfur compounds formed from combustion
of high sulfur fuels are also detrimental and act to
reduce life. These may react in the presence of V and
cause greatly accelerated rates of attack, especially
when the temperature of the metal part exceeds 1200F
(649C). Combinations of Na, S and V compounds are
reported to melt at as low as 1050F (566C). Such deposits are extremely corrosive when molten because of
their slagging action. In these circumstances, 50Cr50Ni or 60Cr-40Ni castings are used to resist corrosion.
References
1. Cullity, B.D., Elements of X-Ray Diffraction, Second
Ed., Addison-Wesley Publishing Company, Inc., Reading,
Massachusetts, 1978.
2. Darken, L.S., The Physical Chemistry of Metallic Solutions and Intermetallic Compounds, Her Majestys Stationery Office, London, England, United Kingdom, 1958.
3. Swalin, R.A., Thermodynamics of Solids, Wiley &
Sons, New York, New York, 1972.
4. Higgins, R.A., Properties of Engineering Materials,
Hodder and Staughton, London, England, United Kingdom, 1979.
5. Bain, E.C., and Paxton, H.W., Alloying Elements in
Steel, Second Ed., American Society for Metals, Metals
Park, Ohio, 1966.
6. McGannon, H.E., Ed., The Making, Shaping and Treating of Steel, Ninth Ed., United States Steel, Pittsburgh,
Pennsylvania, 1970.
7. Lankford, W.T., Jr., et al., The Making, Shaping and
Treating of Steel, Tenth Ed., Association of Iron and Steel
Engineers, Pittsburgh, Pennsylvania, 1985.
8. Long, C.J., and DeLong, W.T., The ferrite content of
austenitic stainless steel weld metal, Welding Journal,
Research Supplement, pp. 281S-297S, Vol. 52 (7), 1973.
9. Boyer, H.E., and Gall, T.L., Eds., Metals Handbook:
Desk Edition, American Society for Metals, Metals Park,
Ohio, 1985.
7-24
18. Morro, H., III, Zinc, Metals Handbook, Desk Edition, pp. 11-l to 11-3, Boyer, H.E., and Gall, T.L., Eds.,
American Society for Metals, Metals Park, Ohio.
19. Hayden, H.W., et al., The Structure and Properties
of Materials, Vol. III, Mechanical Behavior, Wiley & Sons,
New York, New York, 1965.
20. Barsom, J.M., and Rolfe, S.T., Fracture and Fatigue
Control in Structures, Second Ed., Prentice-Hall,
Englewood Cliffs, New Jersey, 1987.
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