High temperature steel
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Molybdenum uses Media centre Health, Safety & Environment
IMOA
High-temperature steel
Molybdenum has been the key alloying element used to
develop creep-resistant ferritic steels for service
temperatures up to 530 °C. Products and components
made of high-temperature steels include
seamless tubing for water boilers and
superheaters, boiler drums, collectors, pumps and
Large steam turbines require
pressure vessels for elevated temperature
creep-resistant steels for
service, and safe, economical operation.
steam turbine heavy shafts with diameter
exceeding 2 meters and weighing more than 100
mt.
The main application areas of creep-resistant steels are power generation and
petrochemical plants, which use all product forms. Steam turbines require large
forgings and castings, whereas pressure vessels, boilers and piping systems require
tubes, pipes, plates and fittings. In addition to high creep strength, other material
properties like hardenability, corrosion resistance, and weldability are also important.
The relative importance of these properties depends on the specific application. For
example, large turbine rotors require steels with good hardenability, whereas power
plant tubing and piping must have good weldability. Even so, the alloys used in these
different applications employ the same mechanisms to improve creep strength.
Molybdenum in solid solution reduces the creep rate of steel very effectively. It slows
the coagulation and coarsening (Ostwald ripening) of carbides during
high-temperature service. The best results in terms of elevated-temperature strength
are obtained by quenching and tempering to produce a microstructure consisting of
upper bainite.
Improved thermodynamic efficiency is the goal that drives the development of power
plant technology, and it requires both improved plant designs and new steels with
better properties to support those designs.
While the efficiency of
sub-critical plants is less
than 40%, Figure 1
shows future ultra-super-
critical (USC) plant
efficiency is expected to
exceed 50%, cutting CO2
emissions per kilowatt-
hour-produced energy
almost in half.
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High temperature steel https://www.imoa.info/molybdenum-uses/molybdenum-grade-alloy-steels...

strength-low-alloy-
steel.php) Figure 1. Effect of operating conditions on efficiency and
emissions of steam power plants.
Heat-treatable plate steel
(/molybdenum-
uses/molybdenum-grade-
alloy-steels-irons/heat- Creep-resistant ferritic steels continue to be the materials of choice for power plants,
treatable-plate-steel.php) oil refineries and petrochemical plants worldwide. They are classified into CMn steels,
Maraging steels Mo steels, low-alloy CrMo steels, and 9-12%Cr steels. Because of the large number
(/molybdenum- of different steel grades, Table 1 includes only a few representatives typical of each
uses/molybdenum-grade- group.
alloy-steels-irons/maraging-
steels.php) Standard high-temperature structural steels
Tool & high speed steel
(/molybdenum- EN designation ASTM Chemical composition (mass%)
uses/molybdenum-grade- grade C Cr Ni Mo V Nb Others
alloy-steels-irons/tool-
high-speed-steel.php) CMn-steels

Molybdenum grade cast P 235 A max. max. max. max. max.

irons (/molybdenum- 0.16 0.30 0.30 0.08 0.30 Cu
uses/molybdenum-grade-
P 355 max. 0.015 –0.10
alloy-steels-
irons/molybdenum-grade- 0.22
cast-irons.php) Mo Steels
16Mo3 0.12 0.25
Molybdenum grade –0.20 –0.35
Superalloys (/molybdenum-
uses/molybdenum-grade- 9NiCuMoNb5-6-4 max. max. 1.00 0.25 0.015–0.045 0.50-0.80
superalloys.php) 0.17 0.30 –1.30 –0.50
CrMo-steels
Molybdenum metal & Alloys
(/molybdenum- 13CrMo4-5 T/P11 0.10 0.70 0.45
uses/molybdenum-metal- –0.17 –1.10 –0.65
alloys.php)
11CrMo9-10 T/P22 0.08 2.00 0.90
Molybdenum chemistry & –0.15 –2.50 –1.20
uses (/molybdenum- 8CrMoNiNb9-10 max. 2.00 0.30 0.90 min. 10x%C
uses/molybdenum- 0.10 –2.50 –0.80 –1.10
chemistry-
uses/molybdenum- 7CrMoVTiB10-10 T/P24 0.05 2.20 0.90 0.20 0.05-0.10
chemistry-uses.php) –0.10 –2.60 –1.10 –0.30
15-70
ppm B
T/P23 0.04 1.90 0.05 0.20 0.02 –0.08 1.45-1.75
–0.10 –2.60 –0.30 –0.30
9-12% Cr-steels
X11CrMo9-1 T/P9 0.08 8.0 0.90–1.00
–0.15 –10.0
X20CrMoNiV11-1 0.17 10.0 0.30 0.80 0.25
–0.23 –12.5 –0.80 –1.20 –0.35
X10CrMoVNb9-1 T/P91 0.08 8.00 max. 0.85 0.18 0.06 –0.10
–0.12 –9.50 0.40 –1.05 –0.25
X11CrMoWVNb9-1-1 T/P911 0.09 8.50 0.10 0.90 0.18 0.06 –0.10 0.90-1.10
–0.13 –9.50 –0.40 –1.10 –0.25
T/P92 0.07 8.50 max. 0.30 0.15 0.04 –0.09 1.50-2.00
–0.13 –9.50 0.40 –0.60 –0.25
T/P122 0.07 10.0 max. 0.25 0.15 0.04 –0.10 0.30-1.70
–0.13 –12.5 0.50 –0.60 –0.30
1.50-2.50

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Table 1: Standard high-temperature structural steels

The variability of chemical composition among the alloys produces a complexity in

microstructure, resulting in different strengthening mechanisms among the alloys, and
creep-rupture strengths that vary by an order of magnitude.
Grades P235 and its Nb-microalloyed variant P355 are typical CMn- steels having a
ferrite-pearlite microstructure. Carbon and manganese are the alloying elements that
most strongly influence the strengths of these steels. The Nb addition in P355 refines
the grain size and results in higher yield strength compared to P235, but the increase
of creep-rupture strength is rather small, as shown in Figure 2(a). Both steels reach
their application limit at 400°C.

In Mo steels, the solution hardening provided by 0.3% molybdenum is the main cause
for the increase of creep rupture strength shown in Figure 2(a). 9NiCuMoNb5-6-4,
widely known as WB 36, shows a dramatic increase of yield strength over 16Mo3,
partly caused by niobium’s grain-refining effect. Additional hardening by copper
precipitation also increases the yield strength.

The variability of chemical composition among the alloys produces a complexity in

microstructure, resulting in different strengthening mechanisms among the alloys, and
creep-rupture strengths that vary by an order of magnitude.
Grades P235 and its Nb-microalloyed variant P355 are typical CMn- steels having a
ferrite-pearlite microstructure. Carbon and manganese are the alloying elements that
most strongly influence the strengths of these steels. The Nb addition in P355 refines
the grain size and results in higher yield strength compared to P235, but the increase
of creep-rupture strength is rather small, as shown in Figure 2(a). Both steels reach
their application limit at 400°C.

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Figure 2. Creep-rupture strength in MPa of heat-resistant steels.

Molybdenum’s strengthening potential cannot be used fully, since creep ductility

decreases strongly with increasing molybdenum content. Another limitation in the
application of Mo steels is decomposition of iron carbides above 500°C, known as
graphitization. A solution to both problems was to alloy with chromium in combination
with molybdenum. In fact, CrMo steels were the first to allow steam temperatures in
power stations to exceed 500°C. The properties of the classical CrMo steels
13CrMo4-5 (T/P11) and 11CrMo9-10 (T/P22) are illustrated in Figure 2(b). The creep-
rupture strengths of these alloys exceed those of the simple Mo steels by a
substantial margin [Figure 2(a)] because of their higher Mo content. CrMo steels form
chromium carbides that are stable above 500°C, which prevents graphitization.
Chromium also improves oxidation resistance at higher temperatures. The newly
developed steels 7CrMoVTiB10-10 (T/P24) and T/P23 shown in Figure 2(b) have
extremely high strength properties. These alloys are based on and have a
microstructure similar to T/P22. Their strengths are raised considerably by additional
alloying with titanium, vanadium and boron in the case of T/P24, and tungsten,
vanadium, niobium and boron in T/P23.

The increase of chromium to above 7% in CrMo steels leads to a group of steels

containing martensite. This microstructure introduces a new element of structural
hardening. Martensite is characterized by a high dislocation density and a fine lath
structure stabilized by M23C6 precipitates. Thus, structural hardening is responsible
for the large increase in strength of X11CrMo9-1, as compared to 11CrMo9-10
[Figure 2(c)]. Further improvements, especially of the creep strength, have been
achieved by alloying with vanadium, niobium, tungsten and boron, as also shown in
Figure 2(c). The introduction of X20CrMoNiV11-1 at the beginning of the sixties
allowed major increases in power plant efficiency. The transformation behavior and
microstructure of this alloy are comparable to those of X11CrMo9-1. The higher
creep-rupture strength of X20CrMoNiV11-1 results mainly from the larger volume of
M23C6 carbides in the microstructure, a result of the alloy's higher carbon content.
The modified 9 % Cr steel T/P91 (EN designation: X10CrMoVNb9-1) invented in the
USA is now used in power plants all over the world, both in new plants and in
refurbishment work of high-pressure/high-temperature piping systems. Although the
carbon content of T/P91 is lower than that of X20CrMoNiV11-1, its creep rupture
strength is distinctly higher. This improvement is achieved by alloying with vanadium
and niobium. T/P91 takes advantage of finely dispersed type MX Nb/V- carbonitride
precipitates for additional strengthening. It was essential to balance the alloy’s
composition because the optimum MX-precipitate dispersion and particle size can be
achieved only by optimizing the Nb/V ratio and nitrogen content. Subsequently, new
steel grades like X11CrMoWVNb9-1-1 (T/P911), T/P92 and T/P122 have been
developed based on T/P91. These grades represent the current state of development

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for creep-resistant ferritic steels.

Ferritic steel grades

appear to reach their
limit at live steam
temperatures around
620°C. Future USC
power plants will need to
use austenitic steels
and, more likely,
superalloys like Inconel
617 in areas of the
highest temperatures
(Figure 3). Such alloys
contain up to 10% Mo.

Figure 3. Materials for main steam pipes in power plants

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