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New Martensitic Steels for Fossil Power Plant: Creep Resistance

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DOI: 10.1134/S0031918X10020110

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ISSN 0031918X, The Physics of Metals and Metallography, 2010, Vol. 109, No. 2, pp. 186–200. © Pleiades Publishing, Ltd., 2010.
Original Russian Text © R.O. Kaybyshev, V.N. Skorobogatykh, I.A. Shchenkova, 2010, published in Fizika Metallov i Metallovedenie, 2010, Vol. 109, No. 2, pp. 200–213.

STRENGTH
AND PLASTICITY

New Martensitic Steels for Fossil Power Plant: Creep Resistance

R. O. Kaybysheva, V. N. Skorobogatykhb, and I. A. Shchenkovab
a
Belgorod State University, ul. Pobedy 85, Belgorod, 308015, Russia
b
Central Research Institute of the Machine Building Technology, ul. Sharikopodshipnikovskaya 4, Moscow,115088 Russia
Received December 2, 2008

Abstract—In this paper, we consider the origin of hightemperature strength of heatresistant steels belong
ing to martensitic class developed on the basis of the Fe–9%Cr alloy for the boiler pipes and steam pipelines
of power plants at steam temperatures of up to 620°C and pressures to 300 atm. In addition, we give a brief
information on the physical processes that determine the creep strength and consider the alloying philosophy
of traditional heatresistant steels. The effect of the chemical and phase composition of heatresistant steels
and their structure on creep strength is analyzed in detail. It is shown that the combination of the solidsolu
tion alloying by elements such as W and Mo, as well as the introduction of carbides of the MX type into the
matrix with the formation of a dislocation structure of tempered martensite, ensures a significant increase in
creep resistance. The steels of the martensitic class withstand creep until an extensive polygonization starts in
the dislocation structure of the tempered martensite(“troostomartensite”), which is suppressed by V(C,N)
and Nb(C,N) dispersoids. Correspondingly, the service life of these steels is determined by the time during
which the dispersed nanocarbonitrides withstand coalescence, while tungsten and molybdenum remain in
the solid solution. The precipitation of the Laves phases Fe2(W,Mo) and the coalescence of carbides lead to
the development of migration of lowangle boundaries, and the steel loses its ability to resist creep.

Key words: martensitic steel, hightemperature strength, carbides, Laves phases

DOI: 10.1134/S0031918X10020110

INTRODUCTION At present, a whole number of largescale research

At present, in the United States, Japan, China, and
European countries coalfired power plants with
ultrasupercritical (USC) steam parameters (Т = 600–
620°С, Р = 250–340 atm) [1–5] are intensely built.
The transition to such steam parameters from the tra
ditional ones (Т = 545°C, Р = 240 atm) makes it pos
sible to increase the efficiency of coalfired power
plants from ~35% to ~44%. This transition became
possible after the development in the United States,
Japan, and Europe of new heatresistant martensitic
steels on the basis of the Fe–9% Cr steel as a result of
intensive R&D works that were carried out for the last
25 years. These steels have not only high creep resis
tance, but also a relatively low cost, which ensures the
high economic efficiency of their use. The other
important merit is a low thermalexpansion coeffi
cient (TEC), which ensures the high cyclic load capa
bility of the power units in which these steels are used.
In the modern boiler constructions, they are employed
as the material for the hightemperature circuits of
superheated steam, collectors, main steam pipelines,
steam turbines. These steels are joined with the classi
cal heatresistant steels of the P22/23/24 types by
composite welds, allowing making heavier parts of the
boilers from pearlitic or bainitic steels, which is of high
economic importance.
projects devoted to the development and implementa
tion of martensitic steels have been initiated in Rus
sian Federation [4]. The machinebuilding and metal
lurgical plants of RF begin to develop the production
of these steels and fabrication of parts from them.
These works are retarded by the lack of technical
information. The aim of this review is to briefly con
sider the latest achievements in the metallurgical
background of martensitic heatresistant steels in the
Russianlanguage literature and to describe the basic
ways for improving the hightemperature properties of
these steels. This review is restricted to the consider
ation of boiler steels. We also do not analyze some
steels with an increased content of Cr of the P122
(Sumitomo) type, since they exhibit only unessential
differences from the steels of the P92 (Nippon Steel)
and P91 types.
CREEP OF MATERIALS:
GENERAL CONCEPTS
The basic characteristic of hightemperature steels
employed in fossil power plants is their resistance to
creep, which is characterized by two quantities: creep
strength, i.e., a constant stress that causes (in a specific
time at an assigned temperature) strain that does not
exceed an assigned magnitude (for example, 1% for
105 h at 600°С); and rupture time.

186
 NEW MARTENSITIC STEELS FOR FOSSIL POWER PLANT
The creep strength is determined by the strain rate
at the second (steadystate) stage. The less the creep
rate and the stronger its functional dependence on the
applied stress, the higher the creep strength. The strain
rate obeys two different laws [6–10]. At low tempera
tures, the deformation behavior of a material is
described by the equation
ε· = B exp ( βσ ) exp ⎛ 
– Q⎞ , (1)
⎝ RT⎠
where ε· is the strain rate, В and β are constants, σ is
the stress at the steadystate stage, Q is the activation
energy for deformation, R is the universal gas con
stant, and T is the absolute temperature [6–11]. In the
hightemperature range, the strain rate is described by
a power law
ε· = Aσ exp ⎛ 
– Q⎞
n tions can rearrange in directions perpendicular to the
, (2)
⎝ RT⎠
where A is a constant, and n is the stress exponent. The
magnitude of n is equal to 1 in the case of viscous
creep; to 2 in the regime of superplasticity; and varies
from 4 to 5 in the region of hot deformation and from
6 to 8 in the region of warm deformation. The transi
tion from hot to warm deformation leads to an
increase in the magnitude of the exponent according
to the rule n = n + 2 [6–10]. Upon the transition from
the warm to cold deformation, the deformation
behavior of material ceases to be described by Eq. (2);
the dependence of the strain rate on the applied stress
begins to obey Eq. (1). Note that the determining rela
tionships (1) and (2) with an identical accuracy
describe the dependence of the strain rate on the
applied stress at n = 7–9 [12]. Consequently, the value
n ~ 8 in Eq. (2) should be considered as a minimum
value at which the material can be employed as high
temperature. For convenience of the graphic repre
sentation, the dependence of the strain rate on the
applied stress at the steady stage of creep is plotted in
logarithmic coordinates, namely, as a normalized
strain rate ε· kT(D1Gb) (where k is the Boltzmann con
stant, D1 is the temperaturedependent coefficient of
lattice diffusion, G is the temperaturedependent
shear modulus, and b is the Burgers vector of disloca
tions) versus the normalized stress σ/G (Fig. 1) [6–11];
if the steadystate stage is absent, then the strain rate
ε· ss is defined as the minimum strain rate upon a pas
sive loading or the maximum flow stress σpeak upon
active load. Figure 2 displays the temperature depen
dence of the activation energy for plastic deformation
Q. For the majority of materials in which the creep rate
is lower than the slip rate, the magnitude of Q in the
region of cold deformation linearly grows with tem
perature until it becomes equal to the activation
energy for pipe diffusion. In the region of warm defor
mation, Q is equal to the activation energy for pipe dif
fusion, while in the region of hot deformation, it
THE PHYSICS OF METALS AND METALLOGRAPHY
187
becomes equal to the activation energy for lattice dif
fusion.
According to the modern concepts [11–14], the
changes in the activation energy and in the determin
ing relationships of creep (1) and (2) with a change in
temperature or applied stresses are connected with
changes in the mechanisms of plastic deformation,
which for the coarsegrained (≥10 μm) materials can
be briefly presented as follows (Fig. 1 and 2).
(1) In the region of low stresses, creep occurs due to
the diffusion of vacancies through the volume of
grains. The activation energy is equal to the activation
energy for lattice diffusion (Nabarro–Herring, or
Harper–Dorn creep). The development of this mech
anism of creep in the process of exploitation of the
hightemperature materials is inadmissible.
(2) In the region of hot deformation, the disloca
plane of their slip through large distances due to the
hightemperature climb, which is controlled by lattice
diffusion. This gives the possibility for dislocations to
bypass obstacles and leads to low values of creep
strength. The regime of hightemperature materials
exploitation cannot coincide with the strainrate–
temperature interval of hot deformation.
(3) In the region of warm deformation, the disloca
tions rearrange to only small distances due to the slow
lowtemperature climb controlled by pipe diffusion.
Under specific conditions, which will be described
below, the regime of exploitation of superalloys can
coincide with the strainrate–temperature interval of
warm deformation.
(4) In the region of cold deformation, the disloca
tions have no possibility to rearrange; during their
motion, they are forced to intersect obstacles. The tem
peratures and stresses corresponding to the operating
conditions for the hightemperature materials must be
located within the interval of cold deformation.
From the viewpoint of the physical mechanisms of
deformation, an increase in the temperature of the
operation of hightemperature materials is achieved
by shifting the boundaries between different tempera
ture–strainrate regimes of deformation (Fig. 1)
toward higher temperatures. The most effective way to
achieve this is the solidsolution alloying with ele
ments that increase the binding force between the
atoms and, correspondingly, decrease the diffusion
rate. Thus, the alloying of aluminum with 6% Cu leads
to an increase in the temperature boundary between
the warm and hot deformation by 200 K [14]. This
means that the solidsolution alloying is an efficient
method of increasing maximum temperature of high
temperature material operation.
Another method of increasing the operating temper
ature is the introduction of dispersed nanoparticles
resistant to the coalescence into the material; this leads
to the appearance of threshold stresses below which no
deformation occurs (Fig. 3) [11–14, 15–17]. In this
Vol. 109 No. 2 2010
188 KAYBYSHEV et al.

10–4

10–5

Cold
10–6 deformation

10–7 Sherby–Burke
criterion
εkT/(D1Gb)

10–8
n=n+2
Warm
–9 deformation
10

n=5
10–10
Hot
–11 deformation
10

10–12
n=1

10–13 Diffusion
creep

10–14

10–4 10–3 10–2

(σ – σth)/G

Fig. 1. Dependence of the normalized strain rate ε· kT/(D1Gb) on the normalized stresses (σ − σth)/G [6] (k is the Boltzmann
constant; D1 is the temperaturedependent coefficient of latlice diffusion; G is the temperaturedependent shear modulus; and b
is the Burgers vector).

case, the deformation behavior of a material is
described by the following equation:
ε· = A [ ( σ – σ th )/G ] exp ( – Q c /RT ),
n
(3)
where σth is the threshold stress. It is assumed [18] that
the magnitude of the threshold stresses is approxi
mately equal to the applied stresses at which ε· = 5 ×
10–8 s–1, and the exponent in Eq. (2) is n > 20 (in
Eq. (3), n has the “true” values that are obtained by
specific calculations [11–14, 15–17] and lie within
the limits of n = 4–8). This means that the dispersed
particles, which are the “sources” of threshold
stresses, suppress lowrate creep. The use of dispersion
strengthening makes it possible to employ the temper
ature–strainrate operating conditions of hightem
perature materials that coincide with the interval of
warm deformation. Dislocations cannot rapidly go
around particles with dimensions of 10–40 nm by
climbing and are forced to overcome them by generat
ing loops, which requires additional stresses, since an
increase in the dislocation length means an increase in
its energy. The threshold stresses are inversely propor
tional to the distance between the particles [11–14,
15–17]. An increase in the fraction of the dispersed
particles of the second phases and/or their refinement

THE PHYSICS OF METALS AND METALLOGRAPHY Vol. 109 No. 2 2010

 NEW MARTENSITIC STEELS FOR FOSSIL POWER PLANT
Q .
Qbd
Cold Warm Hot
deformation deformation deformation
Qpd
Т
Fig. 2. Fig, 2. Temperature dependence of the activation
energy for plastic deformation: Qbd, activation energy for
lattice diffusion; and Qpd, activation f energy or pipe diffu
sion [6].
leads to an increase in the threshold stresses. If we
select the volume, the distribution, and the average
size of particles in such a way that the threshold
stresses will be greater than the applied stresses, then it
is possible to completely suppress the movement of
dislocations. It should, however, be noted that the
threshold stresses suppress only dislocation creep. The
development of diffusion creep leads to the disappear
ance of threshold stresses [19].
Thus, for a hightemperature material to have a
maximum creep strength, it must have a matrix struc
ture consisting of a heavily alloyed solid solution with
distributed dispersed nanosized particles. An increase
in the degree of the alloying of solid solution with ele
ments that reduce the diffusion rate, just as an increase
in the fraction and a decrease in the size of nanoparti
cles must lead to an increase in the operating temper
ature of the hightemperature materials.
The grain size quite significantly affects the heat
resistance of steels and alloys; this is connected with its
strong effect on the rate of diffusion creep, which
occurs at low strain rates. The rate of the most com
mon (Nabarro–Herring) mechanism of diffusion
creep is expressed by the following equation [6–8]:
D 1 σΩ⎞
ε· NH = B NH ⎛ 
 , (4)
⎝ d 2 kT ⎠
where Ω = 0.7b3 is the atomic volume, d is the average
grain size, and BNH = 15 is a dimensional constant.
The rate of diffusion creep is inversely proportional to
d2. Consequently, an increase in the grain size effec
tively reduces the rate of diffusion creep. Correspond
ingly, the condition necessary for high creep strength,
which can be obtained only in the regime of disloca
tion creep, is a large grain size, which makes it possible
to suppress diffusion creep or to move its interval
toward smaller applied stresses.
The rupture time τ is the second most important
characteristic of the creep behavior. In the hightem
THE PHYSICS OF METALS AND METALLOGRAPHY
189
ε, s–1
.
ε ~ σn
Solid
solution
10–6
Material with dispersed
particles
5 × 10–8
σth σ
Fig. 3. Influence of dispersed particles on the dependence
of the strain rate on the applied stresses [6, 15, 16].
perature alloys, in which at grain boundaries there are
no secondphase precipitates with a high (in compar
ison with the matrix) shear modulus, this time is
inversely proportional to the creep rate at the steady
stage (to the minimum creep rate) according to the
Monkman–Grant relationship
t = C/ ε· ss , (5)
where С is a constant. The quantity τ correlates with
the relative elongation during creep. These character
istics have a fundamental importance for the service
properties of hightemperature materials. It is pre
cisely the magnitude of τ that is used for estimating the
life assessment and the allowable stresses for heat
resistant steels [20–21].
The rupture time is determined by many factors
[6–8, 20]; however, the main of these is the formation
of straininduced pores at grain boundaries. This is
related to the operation of grainboundary sliding
(GBS) [6, 22]. The rotation of grains relative to each
other leads to the formation of pores if there is no GBS
accommodation, which is possible due to the diffusion
or/and slip and climb of lattice or grainboundary dis
locations [6, 22]. The possibility for accommodation
during GBS is determined by the grain size and by the
relationship between the critical stresses for slip and
GBS (τs/τgbs) [20]. The small grain size and the low
relationship provide easier accommodation of GBS by
dislocation slip [22].
There are known several mechanisms of pores for
mation at grain boundaries. All of these are connected
with the existence of structural defects at grain bound
aries, such as the facets, which arise as a result of the
intersection of a grain boundary with slip bands
(Fig. 4a), triple junctions, intergranular particles with
a shear modulus greater than that of the metallic
matrix (Fig. 4b), etc. [6, 22]. These defects lead to the
appearance of local stresses upon the displacement of
grains relative to each other as a result of GBS that
Vol. 109 No. 2 2010
190 KAYBYSHEV et al.
(a)
σ
τgbs
Secondary
slip
GBS
Primary
slip
Fig. 4. Mechanisms of pore formation during creep [6, 7, 22]: (a) the formation of pores at grainboundary steps, at the sites of
emergence of slip bands; and (b) the formation of a pore at a particle located at a grain boundary.
cannot be rapidly relaxed, which leads to the appear
ance of pores remaining stable during deformation. It
is worth noting [20] that the probability of the origin of
pores at large hard particles located along grain
boundaries (Fig. 4b) is almost 100 times higher than
the probability of their nucleation at usual grain
boundaries (Fig. 4a). In fact, Eq. (5) is fulfilled if the
pore formation occurs via the mechanism shown in
Fig. 4a. When large undeformable particles are formed
at grain boundaries, the failure occurs at times that are
less than those predicted by Eq. (5). Correspondingly,
the precipitation of large carbides of the M23C6 type at
grain boundaries in heatresistant steels leads to a pre
mature fracture of material.
Thus, to increase the rupture time τ, the following
conditions should be fulfilled.
(1) GBS should be suppressed. This is achieved by
increasing stresses of 105 by the microalloying of high
temperature steels and alloys with boron, which forms
equilibrium segregates at grain boundaries [19], or by
the generation of precipitates of dispersed particles less
than 10 nm in size at and/or near grain boundaries [23].
(2) The decrease in the grain size facilitates accom
modation during GBS; i.e., the optimum grain size of
hightemperature materials is a result of a compromise
between the suppression of diffusion creep and the
need of avoiding pore formation at grain boundaries.
(3) It is necessary to avoid the precipitation of large
solid particles at grain boundaries.
If we avoid a premature failure in the process of
creep as a result of formation and growth of strain
induced pores, then the allowable creep stresses will be
determined by the creep rate and, correspondingly, by
THE PHYSICS OF METALS AND METALLOGRAPHY
σ (b)
σn
pore
τgbs
Cr23C6 or
Fe2W
GBS
pore
the solidsolution alloying and also by the volume
fraction and by the size of dispersed particles.
TRADITIONAL HEATRESISTANT STEELS
During the last 50 years, the main materials for the
boiler tubes and steam pipelines are steels of the pearl
itic class, such as 12Kh1MF, 15Kh1MF, P22 (in the
Englishlanguage literature these steels are referred to
steels of bainitic class [24]) and bainitic steels P23 and
P24 (Tables 1 and 2). Their chemical composition and
the creep stress at which they retain operational capa
bility for 105 h [8–12] are given in Tables 1 and 2. With
all their differences in the chemical and phase compo
sition, these steels have much in common from the
viewpoint of the alloying philosophy, the route of heat
treatment, and the resultant structure. The route of
heat treatment consists of normalization with a subse
quent hightemperature annealing. The normaliza
tion for these steels in the case of thinwall pipes leads
to the formation of bainite or even martensite, i.e., in
fact, quenching. From the viewpoint of the theory of
heat treatment, the final operation for these steels is
hightemperature tempering, during which there
occurs both a complete decomposition of martensite
or of bainite, and a recrystallization. These steels after
the heat treatment before the beginning of exploita
tion have an equilibrium structure, which consists of
polygonal ferrite grains and precipitates of carbides
inside them (Fig. 5a). It should be noted that this leads
to an interesting phenomenon: the regime of heat
treatment affects the short term characteristics of
creep and does not influence the rupture time and the
Vol. 109 No. 2 2010
 NEW MARTENSITIC STEELS FOR FOSSIL POWER PLANT 191

Table 1. Chemical composition of traditional heatresistant steels

Steel C, % Cr, % W, % Mo, %
P22 0.05–0.15 1.9–2.6 – 0.87–1.13
12Kh1MF 0.08–0.15 0.9–1.2 – 0.25–0.35
15Kh1MF 0.1–0.16 1.1–1.4 – 0.9–1.1
P23 0.04–0.1 1.9–2.6 1.45 0.05–0.3
P24 0.05–0.1 2.2–2.6 – 0.9–1.1
Steel V, % Nb, % Si, % Mn, % B, %
P22 – – 0.5 0.3–0.6 –
12Kh1MF 0.15–0.3 – <0.025 0.4–0.7 –
15Kh1MF 0.2–0.25 – 0.17–0.37 0.4–0.7 –
P23 0.2–0.3 0.02–0.08 ≤0.5 0.1–0.6 0.0005–0.006
P24 0.2–0.3 – 0.15–0.45 0.3–0.7 0.0015–0.007

Table 2. Creep strengths on the base of 105 h, calculated using the Larson–Miller criterion [21], and the standard regime of heat
treatment of traditional heatresistant steels

Steel T = 550°C T = 600°C T = 620°C Heat treatment

12Kh1MF 92 MPa 55 MPa – Normalization at 950–980°C + hightemperature tempering at

720–750°C
5Kh1MF 104 MPa 63 MPa – Normalization at 970–1000°C + hightemperature tempering
at 730–760°C
P222 88 MPa3 52 MPa3 <10 MPa Normalization at 900–960°C + hightemperature tempering at
680–750°C
P231 140 MPa 70 MPa <30 MPa Normalization at 1050°C + hightemperature tempering at
740°C
1 Contains additionally 0.03% N allowable stresses, calculated according to an ASME code are 87 MPa at T = 550°C, and 56 MPa at T =
600°C [27].
2
Calculation via the Manson–Haferd criterion [21]
3 Allowable stresses, calculated according to an ASME code, are 49 MPa at T = 550°C and 27 MPa at T = 600°C.

creep strength at longrange tests [22]. The principles
of the alloying of these steels consist of the following.
(1) The introduction of solute alloying elements
such as Cr, Mo, and W decreases the diffusion rate,
which suppresses the dislocation climb. The greatest
effect on diffusion is due to tungsten. Correspond
ingly, the steel P23 demonstrates the maximum creep
strength (Table 2). The precipitation of these elements
from the solid solution into the carbides in the process
of exploitation leads to an acceleration of creep as a
result of activating diffusion and, correspondingly, dis
location climb.
(2) The introduction of vanadium ensures the for
mation of nanodispersed carbides VC (Fig. 2a), which
can withstand the coalescence at Т ≤ 570°С. Corre
spondingly, up to 70% of carbon proves to be bound
into these carbides, which decreases the fraction of
carbides of the (Mo, W)2C and Cr23C6 types. The par
ticles of vanadium carbide hinder the dislocation
motion. The dispersion strengthening due to vana
dium carbides tends to increase with decreasing spac
ing between them and increasing their volume frac
tion. It should be noted that, as a rule, vanadium does
not binds the entire carbon in steel, since carbon
enters into the carbide composition in the weight ratio
of V : C = 4 : 1, while the quantity of carbon in these
steels usually exceeds this relationship.
The steel P22 (Table 1) is alloyed with Cr and Mo,
which are in the solid solution. This ensures the sup
pression of the dislocation climb until Mo, as an ele
ment that has a greater affinity to carbon, forms car
bides of the Мо2C type. Since the Mo : C weight ratio
in this carbide is very high (8 : 1), in the process of
exploitation almost entire molybdenum escapes from
the solid solution into the Мо2С carbides. Unfortu
nately, during the holding at a temperature of 550°С
the Mo2C carbides tend to grow (Fig. 5b), which leads
to the beginning of an accelerated deformation at the

THE PHYSICS OF METALS AND METALLOGRAPHY Vol. 109 No. 2 2010

192 KAYBYSHEV et al.
(a)
V(C, N)
and/or
(Mo,W)2C
Fig. 5. Structure of steels P22 [21] and 12Kh1MF: (a) after tempering; (b) formation of Cr23C6 and the coalescence of carbides
of the М2С type upon a prolonged holding during creep; and (c) formation of zones free of precipitates and coarsening of carbides
that had precipitated at grain boundaries before failure.
third stage of creep. In addition, after the escape of
molybdenum from the solid solution there begins a
precipitation of Cr23C6 carbides at grain boundaries
(Fig. 5c), which strongly increase in size with time.
This leads to the formation of pores and subsequent
failure. Both these factors restrict the exploitation
temperature of the steel P22 to the temperature of the
intense precipitation of the carbide Mo2C, i.e., 550°С.
The strainrate–strain curves ( ε· –ε) of the steel P22
have a usual [6–8] minimum at small degrees to defor
mation that do not exceed 4%, after which the strain
rate increases. An analysis of experimental data [25]
shows that at an exploitation temperature of 550°С in
the interval of working stresses of 40–100 MPa there
can exist threshold stresses (coefficient n > 10). At
stresses of approximately 15 MPa ( ε· = 10–11 s–1), a
transition to diffusion creep begins. Note that in the
range of exploitation temperatures a distinctive feature
of all heatresistant steels, unlike the classic case
(Fig. 1), is the transition from the domain of warm
deformation into that of diffusionrelated creep with a
decrease in stresses, escaping the stage of hot deforma
tion (Fig. 10). Thus, the basic problem in the case of
steel P22 is the instability of the phase composition
during creep as a result of transition of Mo from the
solid solution into carbides, which makes this material
capricious and hardly predictable. The latter is a large
drawback, since it hampers the prediction of the creep
strength for the lifetime of 2 × 105 h on the basis of tests
to 104 h, since all the criteria of predictions for large
periods of operation based on the tests with a small
time of holding, such as the Larson–Miller or Man
son–Haferd ones, proceed from the assumption on
THE PHYSICS OF METALS AND METALLOGRAPHY
(b) (c)
Cr23C6
the structural stability during creep. In particular, it is
the instability of structure that is assumed to be
responsible for the very large (from 104 to 105 h) scatter
in the rupture time in comparison with other steels at
one and the same applied stress [21].
To eliminate this deficiency, a number of new steels
were designed (Table 1 and 2), in which there was used
a decreased quantity of carbon, which could partici
pate in the formation of carbides (Mo, W)2C and
Cr23C6 during creep at the constant total content of C
in steel (steel 12Kh1MF). This was achieved by the
introduction of V, which forms carbonitrides V(C,N)
upon tempering. In addition, the combined concen
tration of Mo and W (∑(Mo + W)) in the solid solution
was increased in such a manner that, even if part of Mo
is spent for the formation of the Me2C carbide during
creep, the remaining ∑(Mo + W) concentration will
be sufficient to suppress diffusion in the solid solution
and, correspondingly, to suppress the dislocation
climb. This approach proved to be very productive.
Thus, the creep strength at 545°C in the 12Kh1MF
steel, in which half the total amount of carbon is spent
for the formation of V(C,N) during tempering, proved
to be higher than that in P22 and, which is most
important, the creep characteristics of this steel are
well predictable on the time base of 105 h [20]. The
drawback of the steel 12Kh1MF is the precipitation of
carbide Cr23C6 during prolonged creep, which can
lead to the failure of the steel. However, in this steel the
accommodation during GBS can easily be ensured,
which determines its high elongation during creep.
The working temperature of steels 15Kh1MF and P24
could be increased to 570°C. In these materials the
high content of molybdenum in the solid solution pre
Vol. 109 No. 2 2010
 NEW MARTENSITIC STEELS FOR FOSSIL POWER PLANT 193

10–1 Ordinary steel

150
600°С
of the P22 type

Stress at failure, MPa

650°С +1W
10–2 +1Mo + 0.2 V +0.8 W
100 +0.08 Nb
+ 0.04N + 0.2V
–3
Strain rate, h–1

10 +0.08Nb

10–4 50
.
Steel of the P23 type εmin
10–5 Strengthening by particle
Steel of type P91/P911/P92
0
Р2 Р24 Р9 Р91 Р911 Р92
10–6 Stabilization by the dislocation
structure of martensite
t 1/10
10–7
10–1 10–2 100 101 102 103 104 ime, h

Fig. 6. Effect of dispersed particles (traditional heatresis Fig. 7. Progress in the development of heatresistant steels.
tant steels) and of the dislocation structure of tempered Data for the P9–P92 steels were borrowed from [31, 32].
martensite (heatresistant steels of new generation) on
creep [29].

1Cr0.5Mo
P22
P9
12Cr1MoV
P91
P911
P92
500 525 550 575 600 625

Fig. 8. Maximum working temperatures for the presently employed and promising heatresistant steels [31, 32].

vents coalescence of V(C,N) during creep. In addi
tion, in the process of exploitation in these steels
instead of Cr23C6 carbides arising at grain boundaries
there precipitate Mo2C carbides distributed uniformly
in the grain bulk, which increases rupture time, since
the probability of pore nucleation along grain bound
aries decreases strongly in this case. It should be noted
that the difference in the content of chromium in
steels 15KH1MF and P24 does not affect significantly
their properties.
As the apex of the development of steels belonging
to this class, the steel P23 should be recognized [25].
The introduction of 1.6% W strongly decreased the
rate of climb of dislocations and practically suppressed
the precipitation of Cr23C6 at grain boundaries. In
addition, the introduction of Nb, which forms
Nb(C,N), made the steel hereditarily finegrained and
made it possible to control the size of the austenitic
grain. The decrease in the upper boundary of the car
bon content to 0.1% made it possible to precipitate,
during tempering, the virtually entire concentration
∑(С + N) present in the solid solution (this steel con
tains 0.03% N) that remained after the formation of
Nb(C,N) in the form of V(C,N). This ensured a very
low creep rate (at 550°С and σ = 100 MPa, the strain
equal to 1% is achieved in 105 h) due to dispersion
strengthening (Fig. 6) and a very long rupture time
(Table 2). The latter is connected with the introduc
tion of boron, which suppresses GBS. In principle,
this steel can be exploited at small stresses even at
600°С (Fig. 7, 8), although the maximum operating
temperature is considered to be 580°С [21, 26–27].
This gives the possibility to create constructions of tra
ditional coalfired power plants with a steam temper
ature (temperature of the pipe in the boiler is higher by
30–50 K) of up to 545°С using traditional heatresis

THE PHYSICS OF METALS AND METALLOGRAPHY Vol. 109 No. 2 2010

194 KAYBYSHEV et al.
Table 3. Chemical composition of new thermotechnical steels of the martensitic class
Steel C, % N, %
P9 ≤0.15 – 8–10
P91 0.08–0.12 – 8–9.5
P911 0.09–0.13 0.04–0.09
P92 0.07–0.1 0.03–0.07
Steel V, % Nb, %
P9 – –
P91 0.18–0.25 0.06–0.1
P911 0.18–0.25 0.04–0.09
P92 0.15–0.25 0.03–0.07
tant steels. It should be noted that the alloying philos
ophy of the steel P23 is close to that of the new steels
of the martensitic class (Table 3). The difference is
mainly in the content of Cr, which influences the crit
ical rate of martensite transformation and the stability
of the dislocation structure of the martensite upon
tempering; i.e., the difference in the creep behavior of
the classical steel P23 (see Table 2) and of the steels
belonging to martensitic class (Table 3) is caused pre
cisely by the difference in the dislocation structure. In
the tempered state, the dislocation density in the steel
P23 (the structure contains regions of tempered mar
tensite with a polygonized dislocation structure
together with bainite [26]) is almost 10–102 times less
than that in steels of the P91 type. An important merit
of the steel P23, as of all traditional steels with an equi
librium structure, is the possibility of exploitation of
welded pipes in boilers without a local heat treatment
of the weld (PWHT).
It seems that at present all the reserves for an
increase in the working temperature for heatresistant
steels with an equilibrium structure are already
exhausted. A further improvement of the characteris
tics of heatresistant steels and, correspondingly, of
the efficiency of coalfired power plants is possible on
the basis of the design of new heatresistant steels with
another philosophy of alloying.
NEW HEATRESISTANT STEELS
BELONGING TO MARTENSITIC CLASS
The design of heatresistant steels of a new genera
tion is based on the fundamentally new approach to
the alloying of the hightemperature materials; to
increase creep strength in these steels, a dislocation
structure is formed there due to a martensitic transfor
mation, which is retained both after tempering and
under creep conditions (Fig. 9) [27–33]. The basic
technological requirement for such steels is the forma
tion of lath martensite upon cooling in air (in the pro
cess of normalization); i.e., these must be steels
belonging to martensitic class. Such steels were
THE PHYSICS OF METALS AND METALLOGRAPHY
Cr, % W, % Mo, %
– 0.9–1.1
– 0.85–1.05
8.5–9.5 0.9–1.1 0.9–1.1
8.5–9.5 1.5–2 0.3–0.6
Si, % Mn, % B, %
0.25–1 0.3–0.6 –
0.25–0.5 0.3–0.6 –
0.1–0.5 0.3–0.6 0.0003–0.006
0.5 0.3–0.6 0.001–0.006
designed on the basis of the Fe–(9–11)% Cr system.
The regime of their heat treatment consists of quench
ing in air, which for the heatresistant steels is tradi
tionally called as normalization, with a subsequent
mediumtemperature tempering. Accordingly, during
heat treatment of steels with 9% Cr there is formed a
tempered lath martensite structure (TLMS); the dislo
cation density in these steels in the tempered state is
>1014 m–2; i.e., these steels are exploited with a non
equilibrium structure, the enhanced internal energy of
which is caused by the increased dislocation density. In
the process of mediumtemperature tempering of the
martensite, the larger part of carbon precipitates in the
form of carbides; the processes of recovery in the dis
location boundaries lead to a decrease in the disloca
tion density from approximately 1015 m–2 to 1014 m–2;
the processes of polygonization and recrystallization
do not start [30–54]. It should be noted that at present
there is no mathematical apparatus that would make it
possible to analyze the deformation behavior during
creep in materials with a TLMS. It only can be
assumed that the enhanced creep strength of these
steels is associated with enhanced threshold stresses
Σ p d
σ th = σ th + σ th , (6)
Σ d
where σ th are the total threshold stresses, σ th are the
threshold stresses connected with the presence of dis
d
persed particles in the structure of steels, and σ th are
the threshold stresses connected with the dislocation
structure. In the literature, there are no models for the
d
valuation of σ th . It can be assumed that these thresh
old stresses are caused by the effect on the dislocation
from longrange stress fields of the dislocation struc
ture, which prevent its instability during creep.
Historically, the first thermotechnical steel P9 of
the martensitic class was designed in the beginning of
1970s [21]. However, it did not find wide application,
since its properties exceeded the properties of the steel
P22 only a little (Fig. 7), which did not compensate
the technological difficulties of its use (argonarc
Vol. 109 No. 2 2010
 NEW MARTENSITIC STEELS FOR FOSSIL POWER PLANT 195

Initial Boundary of packet

austenite
grain
Boundary of block

M23C6 or
(Fe, Cr)2(W, Mo)

MX

Fig. 9. Structure of P92 steel after heat treatment [29].

welding of articles heated to 160–250°С with the sub
sequent local heat treatment of the welds). Its proper
ties are substantially lower than those of the steel P23
(Fig. 7). This is connected with the fact that the alloy
ing of the steel P9 ensures the formation of a marten
sitic structure upon cooling in air, but does not ensure
the retention of the dislocation structure of the tem
pered martensite during creep. This means that this
steel obeys the rule known for traditional heatresis
tant steels: the structure obtained during heat treat
ment does not affect the creepresistance characteris
tics during tests with longrange times if it is unstable
during creep. The greater the structure instability, the
lower the rupture time. This conclusion follows from a
comparison of the creepresistance characteristics of
the steel P9 with those of the traditional heatresistant
steels (Tables 2 and 4).
The basic problem that had to be solved upon the
development of suitable compositions of heatresis
tant steels belonging to martensitic class consisted in
providing stability of the dislocation structure of the
TLMS during creep. It should be noted that the large
part of the boundaries inside the martensitic packets in
these steels are lowangle boundaries [41, 43, 53].
Consequently, any alloying directed toward the stabi
lization of TLMS during creep must ensure the
decrease in the mobility of dislocations, since the
alloying philosophy for guaranteeing stability of low
angle grain boundaries during creep and suppression
of the motion of mobile dislocations are identical. The
basic tasks of alloying for the 9%Cr steels are:
(1) The suppression of the migration of lowangle
boundaries during creep.
(2) The suppression of the migration of grain
boundaries, which are both the former austenite/aus
tenite boundaries and the boundaries of martensite
packets during creep.
(3) The suppression of the migration of special
boundaries during creep.

THE PHYSICS OF METALS AND METALLOGRAPHY Vol. 109 No. 2 2010

196 KAYBYSHEV et al.

Table 4. Stressrupture strengths on the base of 105 h, calculated via the Larson–Miller criterion [21, 55, 60], and the standard
regimes of the heat treatment of new thermotechnical steels of the martensitic class

Steel T = 550°C T = 575°C T = 600°C T = 620°C T = 650°C Heat treatment

P9 80 MPa 58 MPa 45 MPa – – –

P91 141 MPa3 124 MPa 98 MPa3 68 MPa3,4 – Quenching1 from 1040–1090°C + mediumtemperature
tempering at 730–780°C
P911 182 MPa 150 MPa 108 MPa 83 MPa 53 MPa Quenching1 from 1040–1080°C + mediumtemperature
tempering at 750–780°C
P92 180 MPa 164 MPa 120 MPa2 101 MPa2,4 722 MPa Quenching1 from 1040–1080°C + mediumtemperature
tempering at 750–780°C
1
Quenching by cooling in air.
2
Allowable stresses, calculated according to an ASME code, are 70 MPa at T = 619°C and 48 MPa at T = 649°C.
3
Allowable stresses, calculated according to an ASME code, are 66 MPa at T = 593°C, 48 MPa at T = 621°C, and 30 MPa at T = 649°C.
4
625°C.

The first steel for the supercritical steam parame
ters (P91) was developed at the Argon National Labo
ratory on the base of the P9 steel by introduction of 1%
Mo, 0.2% V, and 0.08% Nb. These additives radically
changed the properties of steels belonging to marten
sitic class, which opened a new era in the heatpower
engineering. The precipitation of the carbide VC made
it possible to avoid the occurrence of recrystallization
during creep, suppression of migration of both ran
dom grain boundaries and special boundaries between
the former blocks of packet martensite. The use of the
carbide NbC made the steel hereditarily finegrained,
which facilitated obtaining packet martensite upon
quenching. There appeared a possibility of exploiting
steel P91 at a working temperature of 600°С. It should
be noted that in the literature there is an information
on the possibility of using this steel at 610°С [26].
However, this regime is not recommended by the pro
ducers of pipes [55].
10–5
10–6
Strain rate, s–1
The creep curve of this steel is characterized by a
long transient stage, which can last for 103–104 h
(Fig. 10). Note that the works devoted to the analysis
of the deformation behavior of this steel are rather
scarce. According to available data [56, 57], only the
following can be asserted for sure. The deformation
behavior of the steel at 80 MPa and Т = 600°С is
described by Eq. (2) with n = 10–12 (Fig. 11) [56].
Spigarelli et al. [57] give reasons in favor of the exist
ence of threshold stresses in this temperature–strain
rate interval. An analysis of the deformation behavior
shows that the true threshold stresses in it are lacking.
At the same time, the dependence of the minimum
strain rate on the applied stresses [57] indicate the pos
sibility of existence of threshold stresses in the high
strainrate interval of dislocation creep. In any case,
the determining relationships ((1) or (3)) provide for
the steel P91 the possibility of operation at 600°С. An
important shortage of this steel is the transition to vis
cous creep according to law (4) already at 60 MPa and
600°C (Fig. 11) [39, 56], which, naturally, strongly
limits the operability of this material. This indicates an
active selfdiffusion of iron in this material, which is
extremely undesirable at a working temperature.
It is precisely the high rate of selfdiffusion that

defines the main disadvantages of steel P91. The car

10–7 bides of the MC type prevent migration of highangle
grain boundaries of both the general and special type
10–8 (Fig. 9) during creep. These carbides practically do
not coalesce during deformation (Fig. 12) [43, 58].
However, they cannot restrain lowangle boundaries
10–9 due to the Oswald drag force. Two processes leading to
structural instability occur in this steel during creep:
10–10 –2 the coalescence of carbides of the M23C6 type and the
10 10–1 100 101 102 103 104 precipitation of Laves phases (Fe, Cr)2Mo (Figs. 13,
Time, h 14). After creep for 5 × 104 h, the size of M23C6 carbides
increases almost twofold, from 80 to 160 nm [43,58].
Fig. 10. Typical creep curve for steels of the P91, P911, and The Laves phases do not precipitate during tempering
P92 types. up to 770°C. However, they precipitate intensely dur

THE PHYSICS OF METALS AND METALLOGRAPHY Vol. 109 No. 2 2010

 NEW MARTENSITIC STEELS FOR FOSSIL POWER PLANT
10–3
Р91
10–4 600°C
10–5
10–6
10–7
Minimum creep rate, s–1
10–8
–9 Diffusion
10
creep
10–10
10–11
1 creep
10–12 1 creep conditions at 600°С on the size of MC carbides [43].
10–13
1 10
Stress, MPa
Fig. 11. Variation of the minimum creep rate of steel P91
as a function of stresses [39].
ing creep [30, 34–38, 43, 51, 58]. There is even an
assumption that their precipitation is responsible for
the decrease in the creep rate at the transient stage [35,
41]. The coalescence of the Laves phases with dimen
sions to 0.5 μm leads to the acceleration of creep, since
Mo leaves the solid solution. We believe that it is pre
cisely the decrease in the content of molybdenum in
the solid solution during creep that is the main reason
for the migration of lowangle boundaries, which leads
to a twofold–fourfold increase in the size of packet
martensite blocks and a decrease in the dislocation
density to 2 × 1013 m–2. This leads to a softening of the
steel P91 and an increase in its creep rate. The precip
itation of coarse Laves phases at the boundaries of ini
tial austenitic grains and the intense coalescence (after
the escape of Mo from the solid solution) of the M23C6
carbides located at these boundaries lead to the forma
tion of pores and premature (with respect to the time
determined from Eq. (5)) failure of material.
Thus, to further increase the operating temperature
of the heatresistant steels belonging to martensitic
class it is necessary to ensure the resistance of M23C6
carbides to coalescence and to suppress the precipita
tion of phases of the (Fe, Cr)2(W, Mo) type during
creep. This will make it possible to stabilize the TLMS.
Based on these approaches, steels of the P911 and P92
types were designed, which differ mainly in the Mo/W
ratio. Note that the steel P92 has somewhat better
properties as compared to P911. Below, we consider
the effect of changes in the chemical and phase com
position of material on creep using steel P92 as an
example, since the regularities controlling the struc
THE PHYSICS OF METALS AND METALLOGRAPHY
197
25
P92 – MC 600°C
20
Average particle size, nm
15
10
10 –12 5
1
0 20000 40000 60000
Time, h
Dislocation
Fig. 12. Effect of the time of holding of steel P91 under
100 500 tural processes occurring in these steels during creep
and, correspondingly, their hightemperature proper
ties are close.
In the initial structure (after heat treatment) of the
steels P911 and P92 there exist M23C6 carbides with a
size of 40–50 nm and MC carbides with a size from 20
to 40 nm; the carbonitrides V(C,N) have a platelike
shape; the carbonitrides Nb(C,N) are equiaxed [37].
It should be noted that there were observed precipi
tates of carbonitrides of the M(C,N) type with a size of
10 nm or even less near the boundaries of the former
austenite grains [37]. Such changes in the chemical
composition made it possible to increase the operating
temperature of these steels to 620°С [26]. A factor of
fundamental importance for the stability of the chem
ical and phase composition of steel P92 was the alloy
ing with W and V. The presence of tungsten in the solid
solution substantially slowed down the diffusion rate.
As a result, the transition at 600°C into the region of
diffusion creep occurs only at 16 MPa [39], which is
almost four times lower than in the P91 steel [56]. In
addition, the presence of tungsten substantially slowed
down both the precipitation of the Laves phases during
creep (its fraction does not exceed 1%, and the size is
less than 100 nm even after holding for 5 × 104 h)
(Fig. 14) and the coalescence of the M23C6e23C6 car
bides [43, 59]. The latter is caused by the substitution
of tungsten for part of Cr atoms in the M23C6 carbide.
The smaller (in comparison with Mo and Cr) rate of W
diffusion in the Fe–9% Cr matrix specifies a decrease in
the rate of the coalescence of these carbides (Fig. 13).
Another element that slows down the rate of coa
lescence in the M23C6 carbides is boron (Fig. 13) [29,
37, 46–48, 60]. Its effect is enhanced by the fact that
boron segregates at grain boundaries. This makes it
possible to suppress GBS along them, which increases
rupture time. It is important that the quantity of boron
in the carbides of the M23C6 type precipitated at the
Vol. 109 No. 2 2010
198 KAYBYSHEV et al.
500
M23C6 600°C
Average particle size, nm
400
300
200
P91
100
P92
0 10000 20000 30000 40000 50000
Time, h
Fig. 13. Effect of the holding time under creep conditions
at 600°С on the size of M23C6 carbides in steels P91 and
P92 [43].
former austenitic boundaries is two times greater than
in the same carbides located in the center of grains
[47]; i.e., the introduction of boron suppresses the
coalescence of the M23C carbides that are arranged
precisely along grain boundaries, which makes it pos
sible to exclude the premature failure in the P92 steel
which is connected with the formation of strain
induced pores (cf. steel P91). This ensures better
creepresistance characteristics of steel P92 at Т ≤
620°C (Table 4). Another consequence of the alloying
with ∑(W + B), which suppresses the coalescence of
Me23C6 carbides, is the high stability of the dislocation
structure of the tempered martensite during creep. It is
provided by an effective retardation of dislocation
movement by Me23C carbides, whose size ~100 μm is
retained during creep. This gives the possibility of
increasing operating temperature of steel P92 by 20 K
in comparison with steel P91.
At higher temperatures, the coalescence of car
bides of the M23C6 type and the precipitation of Laves
phases occur, as in steel P91, at 600°C; i.e., it is neces
sary to use new approaches to alloying, directed
toward a further increase in the working temperature
of steels belonging to martensitic class.
CONCLUSIONS
The new steels belonging to martensitic class sub
jected to heat treatment (quenching + mediumtem
perature tempering) have a nonequilibrium troostite–
martensite structure and show high creepresistance
characteristics at temperatures of up to 620°С. The
alloying philosophy, which ensure the serviceability
of these steels for 2 × 105 h at this temperature are as
follows.
(1) The dislocation structure is formed as a result of
a martensitic transformation, which develops during
cooling in air. The stability of the dislocation structure
THE PHYSICS OF METALS AND METALLOGRAPHY
500
Fe2(W, Mo) 600°C P91
Average particle size, nm
400
300
200
100 P92
0 10000 20000 30000 40000 50000
Time, h
Fig. 14. Effect of the holding time under creep conditions
at 600°C on the size of the Laves phases Fe2(W, Mo) in
steels P91 and P92 [43].
of the tempered martensite in the process of creep is
ensured by the suppression of dislocation climb due to
a decrease in the diffusion rate in the solid solution and
the precipitation of dispersed particles. The steel pre
serves high resistance to creep until intense processes
of polygonization and recrystallization are developed.
(2) An increase in the content of ∑(Mo + W) in the
solid solution is an effective method of the suppression
of diffusion and, correspondingly, of climb of disloca
tions. Simultaneously, the high (>1%) content of W
holds in control the coalescence of carbides of the
М23C6 type and slows down the precipitation of the
Laves phases of the (Fe, Cr)2(W, Mo) type during
creep.
(3) The introduction of boron in concentrations of
more than 0.003% ensures its segregation in the M23C6
carbides located at grain boundaries. This substantially
increases the resistance of these carbides to coales
cence, which increases rupture time during creep.
(4) The introduction of V and Nb into steel leads to
the precipitation of nanosized carbonitrides of the MX
type. They suppress the migration of lowangle and
highangle grain boundaries and the movement of dis
locations during creep. Simultaneously, the Nb(C,N)
dispersoids make the steel hereditarily finegrained.
ACKNOWLEDGMENTS
The authors thank the Federal Agency for Science
and Innovations for the support of this work within the
framework of the Federal Project no. 02.523.12.3019
(“Development of Nanostructured HighTempera
ture Steels and Technologies of the Production of
HighTemperature Elements of Power Equipment of
New Generation from These Steels”).
Vol. 109 No. 2 2010
 NEW MARTENSITIC STEELS FOR FOSSIL POWER PLANT
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