Carbide Precipitation in 2.

25 Cr-1 Mo Bainitic Steel:

Effect of Heating and Isothermal Tempering
Conditions
SYLVAIN DÉPINOY, CAROLINE TOFFOLON-MASCLET, STÉPHANE URVOY,
JUSTINE ROUBAUD, BERNARD MARINI, FRANÇOIS ROCH,
ERNST KOZESCHNIK, and ANNE-FRANÇOISE GOURGUES-LORENZON

The effect of the tempering heat treatment, including heating prior to the isothermal step, on
carbide precipitation has been determined in a 2.25 Cr-1 Mo bainitic steel for thick-walled
applications. The carbides were identified using their amount of metallic elements, morphology,
nucleation sites, and diffraction patterns. The evolution of carbide phase fraction, morphology,
and composition was investigated using transmission electron microscopy, X-ray diffraction, as
well as thermodynamic calculations. Upon heating, retained austenite into the as-quenched
material decomposes into ferrite and cementite. M7C3 carbides then nucleate at the interface
between the cementite and the matrix, triggering the dissolution of cementite. M2C carbides
precipitate separately within the bainitic laths during slow heating. M23C6 carbides precipitate at
the interfaces (lath boundaries or prior austenite grain boundaries) and grow by attracting
nearby chromium atoms, which results in the dissolution of M7C3 and, depending on the
temperature, coarsening, or dissolution of M2C carbides, respectively.

DOI: 10.1007/s11661-017-4045-6
 The Minerals, Metals & Materials Society and ASM International 2017

I. INTRODUCTION importance. Various types of carbides with different

LIGHT water reactors are representing 80 pct of the
world nuclear power plants. On an international level,
the renewal of second-generation nuclear power plants is
still to be provided by light water reactors until at least
the middle of the century. Safety and technological
improvements of light water reactors will thus represent
key issues for the next decades. In this framework, a 2.25
Cr-1 Mo steel is being considered as potential candidate
pressure vessel material for future light water reactors.
The two main reasons are its good mechanical proper-
ties in the quenched and tempered condition[1] and its
good resistance to radiation-induced embrittlement
compared to usual pressure vessel steels.[2]
In such material, the precipitation of carbides in the
bainitic matrix during its formation due to quenching
and during the subsequent tempering is of primary
SYLVAIN DÉPINOY is with the DEN-Service de Recherches
Métallurgiques Appliquées, CEA, Université Paris-Saclay, 91191, Gif
sur Yvette, France, and also with the MINES ParisTech, Centre des
Matériaux, PSL Research University, UMR CNRS 7633, BP 87,
91003, Evry Cedex, France. Contact e-mail: sdepinoy@gmail.com
CAROLINE TOFFOLON-MASCLET, STÉPHANE URVOY,
JUSTINE ROUBAUD, and BERNARD MARINI are with the
DEN-Service de Recherches Métallurgiques Appliquées, CEA, Université
Paris-Saclay. FRANÇOIS ROCH is with AREVA, 1 place Jean Millier,
92084, Paris La Défense Cedex, France. ERNST KOZESCHNIK is with
the Institute of Materials Science and Technology, TU Wien, Getreide-
markt 9,Vienna 1060, Austria. ANNE-FRANÇOISE GOURGUES-
LORENZON is with the MINES ParisTech, Centre des Matériaux, PSL
Research University, UMR CNRS 7633.
Manuscript submitted November 22, 2016.
Article published online March 9, 2017
thermal stabilities can be found depending on the
tempering time and temperature, namely, M3C, M2C,
M7C3, M23C6, and M6C.[3] The size, nature, and phase
fraction of carbides have a direct influence on the
mechanical properties of the material, for instance by
improving creep strength[4] and by inducing secondary
hardening.[5] Thus, tight control of carbide precipitation
through manufacturing heat treatments is a key point
for the targeted industrial application.
Pioneering work on carbide precipitation in 2.25 Cr-1
Mo steel was published by Baker & Nutting in 1959,[3]
and can be summarized as follows. Upon tempering, the
cementite M3C is the first type of carbide that precip-
itates, followed by metastable carbides M2C and M7C3.
With further tempering, these three metastable carbides
are replaced by the equilibrium carbides M23C6 and
M6C. This precipitation sequence has been widely
confirmed since then[5–8] for martensitic and bainitic
2.25 Cr-1 Mo steels, with the exception of Vyrostokova
et al.[9] and Janovec et al.[10] who reported that M23C6
carbides dissolve to the benefit of M7C3 carbides in
vanadium-bearing 2.25 Cr-1 Mo steels. However, the
domain of stability of carbides is highly dependent
on the steel composition: for instance, Mn was reported
to accelerate M7C3 carbide precipitation, whereas Si
was reported to accelerate the precipitation of M2C and
to stabilize M6C carbides.[11] While the mechanisms
governing the effects of Mn on M7C3 carbides and of
Si on M2C remain unclear, it is assumed that Si
increases the driving force for the formation of M6C
carbides.[12,13] Increase in the material carbon content

2164—VOLUME 48A, MAY 2017 METALLURGICAL AND MATERIALS TRANSACTIONS A

also tends to favor M23C6 carbides at the expense of
M6C carbides.[14]
All reported studies on carbide precipitation during
tempering focus on the isothermal soakings. However,
in the studied framework of thick components, heating
is an important step of the tempering heat treatment and
can actually take several hours. Anisothermal precipi-
tation of carbides might occur during slow heating and,
thus, influence the full precipitation sequence. In this
work, carbide precipitation in a 2.25 Cr-1 Mo steel has
been studied both during the heating stage and during
the soaking stage of tempering. The effects of time and
temperature of the soaking step on the carbide phase
fraction, spatial location in the microstructure, chemical
composition, and size were investigated. Based on these
observations and on a thermodynamic assessment of
stability of each carbide, the physical mechanisms
underlying the carbide precipitation sequence are then
discussed.
II. MATERIAL AND EXPERIMENTAL
PROCEDURES
A. Material
The material, which chemical composition is given in
Table I, was taken from quarter-thickness of a
280-mm-thick forged ring, fabricated from a hollow
ingot cast by bottom pouring. The ring had been
austenitized, water quenched, and tempered. The mate-
rial was then cut into blanks. To get a homogeneous,
fully bainitic starting microstructure for tempering, the
blanks were further austenitized at 1243 K (970 C) for
1 hour, then cooled at 0.7 K/s using an induction
furnace.[15] This heat treatment results in a mean prior
austenite grain diameter of 30 lm,[16] bainitic packets
with a mean equivalent diameter of 5 lm, and bainitic
Fig. 1—Microstructure of the material before tempering (Optical
microscopy, etchant: 2 pct Nital solution).
Table I. Chemical Composition of the Studied Material (Wt Pct)
C S P Si
0.15 0.003 0.006 0.24
All chemical elements were quantified by optical emission spectrometry, with the exceptions of carbon and sulfur which were analyzed by
combustion infrared absorption.
METALLURGICAL AND MATERIALS TRANSACTIONS A
lath width of about 500 nm.[15] The as-quenched
microstructure, presented in Figure 1, is free from
carbides but contains a non-negligible amount of
retained austenite, which is consistent with the reports
of granular bainite microstructure for 2.25 Cr-1 Mo
steels.[17–19]
Tempering was conducted in a Pyrox furnace at four
different temperatures: 923 K, 948 K, 973 K, and 998 K
(650 C, 675 C, 700 C, and 725 C), for times ranging
from so-called 0 hour (as-heated states) to 24 hours,
with a heating rate set to 0.03 K/s (2 K/min). Samples
were water quenched after tempering.
B. Experimental Microstructural Characterization
Observations were made on carbon extraction repli-
cas, prepared as follows. After polishing, samples were
slightly etched with a 2 pct Nital solution. A carbon
layer was deposited on the surface of the sample using
an Edwards AUTO 306 thermal evaporator. An elec-
trolytic dissolution of the matrix was then conducted.
The chemical composition of the solution was 100 mL
acetylacetone, 10 g tetramethylammonium chloride in
900 mL of methanol, and the potential was set to 1.3 V
at room temperature. Thin films of carbon were then
retrieved on 3-mm-diameter copper grids.
Scanning electron microscopy (SEM) observations
were done on a JEOL JSM7001F SEM, and transmis-
sion electron microscopy (TEM) observations were done
on a FEI Tecnai F20 TEM with a 200 kV acceleration
voltage. Images were acquired with an Orius camera
with a 1-second exposure time using DigitalMicrograph
software. TEM X-ray energy dispersive spectrometry
(EDX) analyses were performed with an a-tilt of 12 deg
and a counting time of 15 seconds. Spectra were
processed using TIA software; only Fe, Cr, and Mo
elements were taken into account for the quantitative
analyses, using their K energy levels. Elemental quan-
tifications were performed using the Cliff-Lorimer ratio
approach, with k-factors for Fe, Cr, and Mo of 1.421,
1.320, and 4.447, respectively. No thickness correction
was applied.
Electro-etching extraction was performed on
100-mm-long rods with a diameter of 10 mm, dipped
in a solution of 90 pct methanol—10 pct HCl under
Argon sparging and electric current. The typical dura-
tion for electro-etching extraction was 24 hours per rod.
Once the matrix was dissolved, the remaining solution
was filtrated using a Buchner funnel with filters with a
maximum hole size of 220 nm. Several filtrations were
necessary for each experiment. Once the precipitates
were separated from the solution containing the dis-
solved matrix, filters were dried for half a day at 333 K
Mn Ni Cr Mo V
0.51 0.17 2.47 1.11 —
VOLUME 48A, MAY 2017—2165
(60 C). The resulting powder was then analyzed by
X-ray diffraction using a Brüker D8 Advance in the
Bragg-Benato mode, using a h2h configuration, a
Cu-Ka radiation (k = 1.540598 Å), a voltage of 40 kV,
and a current intensity of 40 mA. A LynxEye detector
with a 3 deg opening was used, with discrimination in
energy ranging from 0.19 to 0.25 V. X-ray diffraction
(XRD) spectra were acquired over an angular domain
(for 2h) ranging from 13 to 140 deg with a step of
0.02 deg and a counting time of 10 seconds per angular
step. Finally, quantitative phase fractions were obtained
by Rietveld refinements performed with the FullProf
software using crystal structures for carbides that are
gathered in Table II. It should be pointed out that, while
M2C are usually described with an hexagonal struc-
ture,[7,20] it has been proved and confirmed within this
study that this type of carbide is more accurately
described by an orthorhombic cell.[21] Thus, the
orthorhombic cell was used for Rietveld refinements.
However, for practicality reasons, the hexagonal cell
was used to characterize M2C by diffraction pattern
indexing in the TEM.
Potential biases in results induced by the electro-
etching extraction protocol can be due to (1) loss of
precipitates during the electro-etching extraction, (2)
incomplete filtration of the solution, (3) carbides too
small to be resolved in XRD, and (4) deviations induced
by the Rietveld refinements. Among these potential
errors, only point (4) can be quantitatively assessed,
with a relative error between the calculated and the
experimental diffractograms of about 2 pct. The exper-
imental protocol used in this study is known to give
consistent results for carbides phase fraction in 2.25
Cr-1 Mo steels,[12,22,23] with a good agreement with
TEM observations on extraction replicas for M7C3,
M23C6, and M6C carbides which size ranging from
100 nm to 1 lm.[6] In the present study, the evolution of
phase fractions as characterized by XRD measurements
was qualitatively in good agreement with the TEM
observations on carbon extraction replicas. Thus the
quantitative phase fractions were considered in the good
order of magnitude, i.e., an uncertainty of ±0.05 wt pct.
III. RESULTS
A. Assessment of Thermodynamic Stability of Carbides
Thermodynamic calculations were performed on
MatCalc software using the mc_fe_v2.022 database.[24]
The nominal chemical composition considered for the
calculations is the one reported in Table I.
Table II. Crystallographic Structure Used for Rietveld Refinements in XRD Analyses
Carbide Space Group a (Å)
M3C Pnma (62) 5.07
M2C Pbcn (60) 4.75
M7C3 Pnma (62) 4.52
M23C6 Fm-3m (225) 10.60
2166—VOLUME 48A, MAY 2017
The stability diagram of the considered system is
presented in Figure 2. In addition to the ferrite and
austenite phases, the equilibrium carbides, M6C and
M23C6, are represented in full lines. Once these carbides
are suspended, it is possible to calculate metastable di-
agrams to get an insight about the relative stability of all
carbides. The first one, in dashed lines, shows M7C3 and
M2C precipitates. At last, once these carbides are also
suspended, the metastable diagram only displays M3C
carbides (dotted lines).
This approach allows defining the relative stability of
each carbide compared to the others: these predictions
are consistent with the carbide precipitation sequence
reported earlier. Furthermore, it is shown that M2C
carbides are not stable at temperatures higher than
~973 K (700 C) and that M6C carbides are not
expected to be observed, as they are only stable at
temperatures below ~900 K (625 C).
B. Identification of Carbides
In order to characterize the evolution of carbides with
time and temperature on a statistically significant basis,
one had to find a convenient means to readily identify
them. Based on the literature, it appears that each type
of carbide exhibits a particular crystal structure as well
as a characteristic amount of metallic elements, mor-
phology, and nucleation site, as summarized in
Table III.
Fig. 2—Carbide stability diagrams as predicted by MatCalc using
the steel composition reported in Table I.
b (Å) c (Å) Pearson Data Sheet No.
6.74 4.52 1720152
6.02 5.20 1715923
6.97 12.07 1413617
10.60 10.60 1901808
METALLURGICAL AND MATERIALS TRANSACTIONS A
 Table III. Carbide Characteristics From Available Literature Data[3,6,8,14,20,25–32]

Carbide Morphology Metallic Elements Nucleation Site

M3C lenticular, globular Fe-rich with Cr interfaces
M2C needle-like Mo-rich with Cr laths
M7C3 rhombus-shaped, rod-like Cr-rich with Fe interfaces
M23C6 rod-like Fe-rich with Cr interfaces/laths
M6C globular Mo-rich with Fe interfaces
‘‘Interfaces’’ stands for prior austenite grain boundaries and lath boundaries, while ‘‘laths’’ stands for the matrix or dislocations.

Fig. 3—Ternary representation of the chemical amount in metallic elements in carbides after tempering at 948 K (675 C) along with bright-field
TEM observations on carbon extraction replica of the corresponding carbides. Calculations were performed with the MatCalc database. Chemi-
cal composition of M7C3 and M2C carbides were calculated by suspending M23C6 and M6C carbides.

Experimentally analyzed carbides could be catego-
rized into four different groups according to their
metallic element content and their morphologies as
shown in the example of Figure 3: lenticular iron-rich
carbides, rod-like iron-rich carbides with some chro-
mium, rhombus-shaped or globular chromium-rich
carbides with some iron, and molybdenum-rich carbides
that were mostly needle-like but can also be encountered
as globules.
When comparing these compositions and morpholo-
gies with the typical composition determined by Moss &
Kelly,[27] thermodynamic calculations for the given
temperature [in this case, 948 K (675 C)] and literature
data as reported in Table III, it appears clearly that these
four groups represent M3C, M23C6, M7C3, and M2C
carbides, respectively. To confirm these observations,
electron diffraction patterns were obtained for different
carbide morphologies, as shown in Figure 4. Due to the
small size of M2C carbides, conventional electron
diffraction patterns were difficult to obtain. Thus, index-
ation of the crystal structure for these carbides was
performed on Fast Fourier Transform (FFT) images
from HRTEM images, which contains similar informa-
tion to electron diffraction patterns when a single crystal
is taken into account.[33] Good agreement was found with
EDX characterizations: needles were orthorhombic
M2C, diffraction pattern of rhombus-like particles exhib-
ited streaks associated to stacking faults that are char-
acteristic of orthorhombic M7C3,[14,34] and rod-like
particles were cubic M23C6. No pattern was taken from
M3C due to their rarity. Each one of these carbides was
encountered at specific microstructural sites: cementite,
M23C6, and globular M7C3 were mostly found at
interfaces, whereas M2C and rhombus-shaped M7C3
were encountered in the matrix. Gope et al. determined
that the M23C6 carbides follow a Nishiyama–Wassermann
orientation relationship with the bainitic matrix, where
(001)a // (011)M23C6 and ð120Þa//ð211ÞM23C6, and
that M2C carbides and the bainitic matrix follow a
(101)a ~5 deg from ð11:1ÞM2C and (233)a ~5 deg
from (11.0)M2C orientation relationship, assuming a
pseudo-hexagonal structure for the carbide.[30] No orien-
tation relationships between the carbides and the matrix
were determined in this study, since all TEM observations
were made on carbon extraction replicas. However, the
carbides identified as M2C clearly followed the regular
Windmanstätten pattern in the matrix already outlined by
other authors.[8,28]

METALLURGICAL AND MATERIALS TRANSACTIONS A VOLUME 48A, MAY 2017—2167

Fig. 4—(a) Bright-field High-Resolution TEM image of an M2C carbide, (b) corresponding FFT image, (c) Bright-field TEM image of an M7C3
carbide, (d) corresponding diffraction pattern, (e) Bright-field TEM image of an M23C6 carbide, (f) corresponding diffraction pattern. Observa-
tions on carbon extraction replica, tempering: 948 K (675 C)—5.5 h. M7C3 and M2C are identified here using their hexagonal unit cells.

These observations are consistent with the data
reported in literature; hence, TEM-EDX analysis on
carbon extraction replicas was chosen as a fast and
efficient way to characterize the nature, size, and
chemical composition in metallic amount as a function
of tempering conditions.
In the present study, these four types of carbide were
found for almost each tempering condition, and the
specific case of M3C morphology will be discussed later.
No M6C carbide was ever observed, consistently with
thermodynamic equilibrium calculations, and with lit-
erature data: the occurrence of M6C in 2.25 Cr-1 Mo

2168—VOLUME 48A, MAY 2017 METALLURGICAL AND MATERIALS TRANSACTIONS A


(a) (b) (c)
Fig. 5—XRD spectra on bulk samples showing the austenitic {111}
planes and the ferritic {110} planes: (a) as-quenched sample, (b) he-
ated up to 673 K (400 C) then water quenched, (c) heated up to
873 K (600 C) then water quenched.
was usually reported after aging or after long-time
service, namely, for temperatures below 923 K (650 C)
and for time durations up to more than
20 years,[6,25,29,30,32] while they were not reported for
short times (<20 hours) at higher temperatures.[26,30]
C. Carbide Precipitation Upon Heating
X-ray diffraction on the as-quenched sample prior to
tempering shows that the material contained a certain
amount of retained austenite, which is consistent with
the typical granular bainite microstructure observed for
2.25 Cr-1 Mo steels.[17–19] Decomposition of this
retained austenite during heating was studied by X-ray
diffraction on bulk samples. Partial XRD spectra
obtained on samples heated at 0.03 K/s up to 673 K
and 873 K (400 C and 600 C), respectively, and then
water quenched are presented in Figure 5. They show
that austenite had started to decompose at 673 K
(400 C) and that the transformation was complete at
873 K (600 C), for the (slow) heating rate used here.
Observations by TEM of carbon extraction replicas did
not reveal the presence of carbides for the sample heated
up to 673 K (400 C). Either precipitated carbides were
too small to be observed or they were too coherent with
the matrix to be successfully transferred to the carbon
replica. No observation was made for the sample heated
up to 873 K (600 C).
Figure 6 shows SEM observations of carbon extrac-
tion replicas of samples heated up to 923 K, 948 K,
973 K, and 998 K (650 C, 675 C, 700 C and 725 C).
Samples were immediately water quenched as soon as
they reached the targeted temperature. At 923 K
(650 C), large clusters of carbides were observed at
the interfaces such as prior austenite grain boundaries
and lath boundaries. These clusters densified at 948 K
(675 C), then started to disappear at 973 K (700 C)
and were almost fully dissolved at 998 K (725 C). At
this temperature, prior austenite grain boundaries were
mostly decorated with globular M7C3 carbides and few
rod-like M23C6. Along with these clusters, some isolated
METALLURGICAL AND MATERIALS TRANSACTIONS A
carbides were also found within the laths for all four
states, in an increasing number as the temperature
increased.
Many carbide clusters appeared to be iron-rich and
depleted in molybdenum. With increasing temperature,
they tended to get enriched in chromium. On the whole,
these clusters remained within the composition range for
cementite, and got enriched in chromium with increas-
ing time. Such occurrence of ‘‘branch-like’’ cementite
resulting from the decomposition of retained austenite
has already been reported.[3,8,28]
Isolated carbides were either iron-rich (cementite) or
molybdenum-rich (M2C) or iron-rich with some chro-
mium enrichment, depending on the temperature
reached before quenching. Cementite was predomi-
nantly found at temperatures lower than 998 K
(725 C). No EDX chemical composition measurement
was made on M2C at 923 K and 948 K (650 C and
675 C) due to their too small dimensions; moreover,
they were rarely seen at 923 K (650 C). It is also
interesting to notice that M2C were mostly chromium-
rich at 973 K (700 C). M7C3 and M23C6 carbides were
present in all four conditions; however, their composi-
tion could only be determined with certainty at 998 K
(725 C) where they were iron-richer than expected. At
lower temperatures, a whole set of analyzed carbides
were too rich in chromium to be M23C6, but not rich
enough to be characterized as M7C3. Thus, their nature
remained uncertain at that stage and will be discussed
later.
D. Carbide Evolution Upon Tempering: Effect of Time
and Temperature
1. Evolution of phase fractions
In order to quantify the evolution of the different
carbides for isothermal and isochronous tempering
conditions, respectively at 948 K (675 C) and for
5.5 hours, the powder extraction residues obtained by
electro-etching were systematically analyzed by XRD.
The amounts of phases were determined by Rietveld
refinements of the spectra. Results are shown in
Figure 7. M3C carbides were predominant at the end
of the heating up to 948 K (675 C), in good agreement
with the TEM observations made in the previous
section. With further tempering time, they dissolved
gradually (Figure 7(a)). The M7C3 phase fraction
increased during the first 5.5 hours of tempering and
slightly decreased for longer times. On the other hand,
the fraction of M23C6 carbides kept increasing with
time, particularly during the first 3 hours. The M2C
carbide phase fraction tended to remain stable.
After tempering for 5.5 hours, the weight fraction of
cementite was the same at 923 K, and 948 K (650C and
675C), while cementite was fully dissolved at 973 K and
998 K (700 C and 725 C). M7C3 carbide weight
fraction did not seem to be directly correlated with the
holding temperature. On the other hand, the M23C6
fraction increased with the holding temperature, and
stabilized at 973 K (700 C). The weight fraction of
M2C decreased with temperature.
VOLUME 48A, MAY 2017—2169
Fig. 6—Secondary electrons SEM observations on carbon extraction replicas of samples heated at 0.03 C/s then water quenched. (a) 923 K
(650 C), (b) 948 K (675 C), (c) 973 K (700 C), (d) 998 K (725 C), (e) detail of (b) showing a massive cluster, (f) detail of (d) showing M7C3 at
the prior austenite grain boundaries and M2C and M23C6 carbides in the matrix.

2. Evolution of size and morphology
Figure 8 shows typical TEM micrographs taken from
carbon extraction replicas after tempering at different
temperatures for 3 and 24 hours.
Cementite clusters remained in the material after
3 hours at 923 K and 948 K (650 C and 675 C), and
remnants of these clusters could still be found after
5.5 hours at these temperatures. For longer durations and
higher temperatures, these clusters had spheroidized and
all observed cementite was globular. Moreover, they
became rarer with increasing time and temperature. After
tempering for 24 hours, no cementite was ever observed.
M7C3 carbides had a fairly constant size, with an
equivalent diameter of around 100 nm. No M7C3 was

2170—VOLUME 48A, MAY 2017 METALLURGICAL AND MATERIALS TRANSACTIONS A

 (a) (b)

Fig. 7—Evolution of carbide weight fraction during tempering (a) with time at 948 K (675 C), (b) at different temperatures after tempering for
5.5 h.

Table IV. Summary of Available Literature Data on the Amount of Chromium and Molybdenum in Solid Solution in 2.25 Cr-1
Mo Steels

Ref. Heat Treatment C in Steel (Wt Pct) Cr in Solid Solution Mo in Solid Solution
7 923 K (700 C)—24 h 0.12 73 pct (1.55 wt pct) 74 pct (0.74 wt pct)
35 tempered and aged for up to 30,000 h at 700 K, 0.15 73 pct (1.80 wt pct) 60 pct (0.65 wt pct)
727 K and 755 K (respectively 427 C, 454 C,
and 482 C)
36 923 K (650 C)—10 h 0.2 62 pct (1.60 wt pct) 50 pct (0.50 wt pct)
37 1003K (730C)—1 h 0.08 90 pct (1.93 wt pct) 77 pct (0.77 wt pct)
Similar percentages (normalized by the total amount in the material) result in different amounts depending on the reference, due to differences in
the chromium and molybdenum content in the steels.

observed after tempering at 998 K (725 C) for
24 hours.
M23C6 carbides were hardly found after 3 hours at
923 K (650 C), whereas they were readily observed in
all other tempered states. They tended to grow after
longer tempering times and at higher temperatures.
Interestingly, they seemed to lengthen with increasing
temperature, and to lengthen and widen with increasing
time.
M2C carbides were predominantly found as needles
for shorter times and at lower temperatures, even if
globular M2C were also found. At 923 K (650 C), their
number fraction tended to increase with time, while at
948 K (675 C) it seemed to slowly decrease and needles
seemed to widen. The same phenomenon was observed
at 973 K and 998 K (700 C and 725 C) for time
durations shorter than 12 hours. For longer times,
needles were rarely seen while globules were still found,
and, after 24 hours, only globules were observed. The
maximal length of needles remained around 100 nm.
Moreover, an M2C-free zone was observed in the
vicinity of M23C6 carbides located at interfaces, regard-
less of tempering conditions. At 948 K (675 C), this
precipitate-free zone sized fairly 500 nm, regardless of
tempering time.
3. Evolution of the chemical composition of carbides
The relative amount of metallic elements, i.e., the
weight percentage of iron, chromium, and molybdenum
in the M constituent of M7C3, M23C6, and M2C carbides
were analyzed after all 20 heat treatments. Figure 9
shows the evolution of metallic amounts with time at
923 K and 998 K (650 C and 725 C) for M7C3,
M23C6, and M2C carbides along with their pseudo-equi-
librium composition as predicted by MatCalc. For
better clarity, chemical compositions are represented
by the two major metallic elements in each considered
carbide. Molybdenum content for M7C3 and M23C6 and
iron content for M2C remained relatively constant with
time and temperature, respectively ranging between 9
and 13 pct, 13 and 17 pct; and 2 and 5 pct in weight.
Initial chemical compositions for M7C3, M23C6, and
M2C are only shown at 973 K and 998 K (700 C and
725C) for the reasons previously explained.
Analyses for cementite are not represented due to the
low number of analyzed precipitates for temperatures

METALLURGICAL AND MATERIALS TRANSACTIONS A VOLUME 48A, MAY 2017—2171

Fig. 8—Bright-field TEM observations on carbon extraction replicas after tempering under various conditions. White, light gray, dark gray, and
black arrows show examples of M3C, M2C, M7C3, and M23C6 carbides, respectively.

higher than 948 K (675 C) and time durations longer
than 12 hours. After three hours of tempering, their
chemical composition remained stable with time and
temperature, typically 70 pct Fe, 25 pct Cr, and 5 pct
Mo, in wt pct. At 923 K and 948 K (650 C and
675 C), enrichment by 12 and 5 pct in chromium,
respectively, at the expense of iron took place upon the
first 3 hours of tempering.
At all temperatures, M7C3 carbides became enriched in
chromium and depleted in iron with increasing time before
stabilizing, which tended to evolve their chemical
composition closer to pseudo-equilibrium, which was,
however, never reached. This was particularly obvious at
923 K and 973 K (650 C and 700 C). Moreover, stabi-
lization seemed to occur for shorter times at higher
temperature: not before 24 hours at 923 K (650 C), and
between 3 and 5.5 hours at 998 K (725 C). After further
tempering up to 12 hours at 998 K (725 C), M7C3 carbides
were enriched in iron at the expense of chromium, thus
moving away from their pseudo-equilibrium composition,
and they were even absent after 24 hours of tempering at
this temperature, as already stated in the previous section.

2172—VOLUME 48A, MAY 2017 METALLURGICAL AND MATERIALS TRANSACTIONS A

Fig. 9—Relative iron content as a function of the relative chromium content in the M constituent of M7C3 and M23C6, and relative chromium
content as a function of the relative molybdenum content in the M constituent of M2C for various tempering times at 923 K and 998 K (650 C
and 725 C). EDX analyses on carbon extraction replicas. Equilibrium values predicted with MatCalc. Chemical composition of M7C3 and M2C
carbides were calculated by suspending M23C6 and M6C carbides.

METALLURGICAL AND MATERIALS TRANSACTIONS A VOLUME 48A, MAY 2017—2173

 (a) (b)
Fig. 10—Evolution of the percentage of chromium, molybdenum, and carbon in solid solution (normalized by their total amount in the mate-
rial) (a) during tempering at 948 K (675 C) and (b) after 5.5 h at several temperatures.

Unlike that of M7C3, the chemical composition of

M23C6 appeared more stable with time at all tempera-
tures, with the exception of the first 5.5 hours at 923 K
(650 C), where a clear enrichment in chromium
occurred at the expense of iron. However, at all
temperatures, a slight average enrichment in chromium
seemed to take place between 3 hours and 24 hours.
Their chemical composition was always close to the
equilibrium one, and became closer as the holding
temperature was higher. After 24 hours of tempering at
998 K (725 C), M23C6 carbides had clearly reached
their equilibrium composition.
The amount of chromium evolved linearly with the
amount of molybdenum for M2C carbides for all
conditions (Figure 9). This was due to the very low
iron content (<5 wt pct) in these carbides, which only
changed very slightly with tempering time and temper- Fig. 11—Ternary representation of the evolution of carbide chem-
ature. The M2C composition was rather scattered for istry at the end of heating. The center circle shows the unidentified
short times and low temperatures. For instance, after carbides formed at 973 K (700 C), the bottom circle highlights the
5.5 hours of tempering at 973 K (700 C), it ranged M7C3 carbides formed at 998 K (725 C) and the top circle M23C6
carbides formed at 998K (725 C). The arrows pointing upward and
from 50 pct Mo-45 pct Cr to 90 pct Mo-7 pct Cr. A downward, respectively, represent potential enrichment in iron and
clear correlation was found between the composition chromium.
and the morphology of M2C carbides: needles were
mostly chromium-richer, while globules were molybde-
num-richer. However, needles tended to enrich in and isochronous soakings for 5.5 hours. Errors were
molybdenum with increasing time and temperature, calculated by taking into account standard deviations in
too. Like M23C6 carbides, M2C carbides approached the relative amount in metallic elements as determined
their pseudo-equilibrium composition, and reached it by TEM-EDX, the experimental error associated with
for shorter times as the tempering temperature increases. the electro-etching extraction protocol and the uncer-
tainties associated with the chemical analysis reported in
4. Elements in solid solution Table I (respectively 0.005 wt pct for carbon and 0.03
By combining the chemical content in carbides wt pct for chromium and molybdenum).
obtained by EDX measurements and the phase fraction The fraction of chromium and molybdenum in solid
as determined by Rietveld refinements, one can calculate solution seems to be time and temperature independent,
the amount of iron, chromium, and molybdenum at least for tempering times longer than 3 hours. About
contained in carbides and therefore the amount con- 70 pct of the total chromium and molybdenum atoms
tained within the bainitic matrix. By assuming that are in solid solution, that is, respectively 1.8 and
carbides are stoichiometric, the amount of carbon can 0.7 wt pct. These results are in good agreement with
also be determined. Figure 10 shows the percentage of the ones reported in the literature, gathered in Table IV.
chromium, molybdenum, and carbon atoms in solid The lower amount of molybdenum in solid solution in
solution based on the chemical composition given in Reference 35 can be explained by the precipitation of
Table I for an isothermal tempering at 948 K (675 C) molybdenum-rich M6C carbides during aging. The

2174—VOLUME 48A, MAY 2017 METALLURGICAL AND MATERIALS TRANSACTIONS A

Fig. 12—Schematic drawing of the carbide precipitation sequence in a prior austenite grain during tempering. Time or/and temperature increases
from (a) to (d), (a) being the end of the heating step and (d) the thermodynamic equilibrium. (a) Extensive precipitation of M3C carbides and
nucleation of M2C, M7C3, and M23C6 carbides. (b) Dissolution of M3C due to the nucleation and growth of M7C3 carbides. End of the nucle-
ation step for M2C and M23C6 carbides, growth of M23C6 carbides begins. (c) Partial dissolution of metastable carbides M7C3 and M2C due to
continued growth of M23C6 carbides. Potential coarsening of the remaining M2C carbides. (d) Full dissolution of M7C3 and M2C carbides, only
M23C6 carbides remain in the material. Black lines delineate lath/packet/austenite grain boundaries.

overall lower and higher amounts of elements in
References 36 and 37, respectively, are likely related to
the amount of carbon in the steels, which has a direct
effect on the phase fractions of carbides. While it is not
shown in Figure 10, it must be pointed out that the
amount of iron in the precipitates decreases with
increasing time and increases with increasing tempera-
ture. This is easily explained by the enrichment in
chromium of M23C6 with increasing time, and by the
shift toward higher iron content in the equilibrium
composition of M23C6 carbides with increasing temper-
ature (Figure 9).
The fraction of carbon remaining in solid solution
ranges from 5 to 20 pct of the total carbon in the
material, that is, between 0.008 and 0.025 wt pct. It was
first assumed that once the precipitation of carbides
starts, all of the carbon is contained within these
carbides, and no more carbon is found in the matrix.
The obtained values are in good agreement with such
assumption, considering the experimental uncertainties,
the fact that a very low amount of carbon may still be
trapped in dislocations and potential freezing of diffus-
ing carbons in the matrix during the water quench that
follows the tempering.

METALLURGICAL AND MATERIALS TRANSACTIONS A VOLUME 48A, MAY 2017—2175

 As a direct consequence of these observations, the
amount of metallic elements in carbides measured by
TEM-EDX and the quantitative phase fraction of
carbides determined by the electro-etching extraction
coupled with XRD measurements can be considered as
reliable.
IV. DISCUSSION
A. Interactions Between Different Types of Carbide
1. M3C carbides
M3C carbides precipitate upon heating in the form of
large clusters stemming from the decomposition of
retained austenite between 673 K and 873 K (400 C
and 600 C). They are thus intimately related to the
starting bainite microstructure. For cementite clusters
being discretely distributed at the interfaces, one can
safely assume that retained austenite was located there,
too. No TEM observations on thin foils on the
as-quenched sample were made to validate this hypoth-
esis. However, such spatial distribution of retained
austenite is consistent with the granular bainite
microstructure usually reported for bainitic 2.25 Cr-1
Mo steel grades.[17–19]
Clusters rapidly spheroidize upon further heating, and
completely disappear at 998 K (725 C). Some of them
can still be found after 3 hours of tempering at
temperatures lower than 973 K (700 C). Then, they
progressively dissolve.
2. M2C carbides
M2C carbides have already precipitated during heat-
ing up to 923 K (650 C) and then grow upon further
heating. They appear to nucleate homogeneously in the
matrix, as suggested by their fine distribution and their
particular orientation relationship with the matrix.
At 973 K and 998 K (700 C and 725 C), M2C are
thermodynamically unstable. Their phase fraction
decreases with increasing tempering time, and only rare
globular M2C are found after 12 hours. The higher
stability of globular M2C might be due to their
particular shape, resulting in a better surface/volume
ratio compared to needles.
At lower temperatures, their phase fraction remains
constant although their number fraction seems to
decrease and M2C needles are widening. This suggests
that coarsening takes place, together with enrichment in
molybdenum and depletion in chromium.
3. M7C3 carbides
The evolution of M7C3 carbides can be described in
three distinct steps: nucleation and growth upon heat-
ing, further increase in phase fraction during the first 5.5
hours of tempering and dissolution for longer tempering
times.
After heating up to 948 K (675 C), M7C3 carbides
are detected by XRD in the dissolution residues, but
none of the carbides analyzed by TEM-EDX could be
identified as M7C3 based on their chemical composition.
At 973 K and 998 K (700 C and 725 C), M7C3
2176—VOLUME 48A, MAY 2017
carbides are observable by means of SEM and TEM,
although their chemical composition could only be
determined at 998 K (725 C), and is iron-richer than
expected. To solve the issue of the origin and chemistry
of M7C3 carbides, one must recall that at lower
temperatures, unidentified carbides were observed to
have a chemical composition within the range of both
M23C6 and M7C3 (see the central circle in Figure 11).
These carbides are unlikely to be chromium-rich M23C6
since this would imply a further enrichment in iron that
would move carbides away from their equilibrium
composition (the upward pointing arrow in Figure 11).
More likely, these carbides are M7C3, suggesting that
they nucleated with a composition far from equilibrium
and then enriched in chromium with further heating
(downward pointing arrow in Figure 11). This increase
in chromium content was also observed during the first
steps of the isothermal holding stages [for instance, after
5.5 hours at 923 K (650 C) and after 3 hours at 973 K
(700 C)].
Moreover, the appearance of observable M7C3 and
their enrichment in chromium seem to coincide with the
spheroidization of M3C clusters, and both carbides are
found at the same location (mostly at interfaces). Thus,
the clusters observed at 948 K (675 C) could actually
consist of a mixture between cementite and iron-rich
M7C3 in their first stages of growth. Once nucleated,
M7C3 particles would then grow by attracting chromium
atoms contained in the bainitic ferrite and neighboring
cementite, triggering its dissolution. Such in situ trans-
formation of cementite into M7C3 was already reported
in 2.25 Cr-1 Mo steels[13,38]; particularly, Biss & Wada
experimentally detected irregular films of M7C3 carbides
in the clusters of cementite after 20 years at 797 K
(524 C) in 1 Cr–0.5 Mo steel.[20] More generally, in
Cr-Mo steels, Inoue & Masumoto reported experimen-
tal evidence that M7C3 carbides nucleate at the interface
between matrix and cementite while maintaining crystal
orientation relationship with cementite before growing
rapidly towards the cementite crystal.[39] This in situ
transformation can be explained by the higher content
in chromium at the interface between the matrix and the
cementite compared to the one in the matrix. Indeed, the
chromium-richer clusters analyzed by EDX after heat-
ing up to 948 K (675 C) contained around 20 wt pct
Cr, which is almost ten times higher than the weight
fraction of the matrix (2.47 wt pct in average without
any precipitation). Thus, when accounting for a single
cementite particle and its surrounding matrix, nucle-
ation of M7C3 at this interface appears to be likely.
During isothermal holding at 948 K and 998 K
(675 C and 725 C), the phase fraction of M7C3
carbides reaches a maximum, and then slowly decreases.
This evolution accelerates with increasing the holding
temperature, as final dissolution occurs between 12 and
24 hours at 998 K (725 C). At all temperatures, no
growth or coarsening seems to occur, their equivalent
circle diameter remaining at ~100 nm. Unlike cementite,
while not being equilibrium carbide, M7C3 is expected to
be present in the studied 2.25 Cr-1 Mo steel for
practically reasonable tempering conditions.
METALLURGICAL AND MATERIALS TRANSACTIONS A
 4. M23C6 carbides
M23C6 were originally thought to form by in situ
nucleation, either within the cementite particles or at the
interface between cementite and matrix.[3] However,
Nutting later considered that these carbides nucleate
separately despite the fact that they are chromium
carbides, since their crystal structure allows them to
readily dissolve more iron than M7C3 and, thus, they need
less chromium to precipitate.[38] This assumption could
explain why M23C6 in 2.25 Cr-1 Mo steels are iron-rich
despite being chromium-based carbides. An additional
reason could be that the interfacial energy of precipitates
that have compositions closer to the one of the surround-
ing matrix, have lower interface energy, which is approx-
imately quadratically dependent on the composition
difference between precipitate and matrix.[40]
M23C6 are equilibrium carbides, since they grow with
increasing tempering time and temperature, while their
chemical composition remains stable and close to that
calculated at equilibrium. While iron atoms are readily
available from the matrix, it is interesting to notice that
the amount of chromium in solid solution remains
constant during the growth of M23C6 carbides, while
simultaneously the chromium amount in M2C decreases
and the M7C3 carbides are dissolving. This indicates that
diffusion of chromium atoms from the less stable car-
bides toward M23C6 carbides takes place, leading to the
dissolution of those less stable carbides.
The correlation between growth of M23C6 and disso-
lution of M7C3 is obvious. However, the constant size of
M7C3 particles suggests that their decrease in volume
fraction is due to a decrease in their number density. In
other words, dissolution of M7C3 is localized. TEM
observations showed that none or few of these carbides
were found near M23C6 carbides for long durations/high
temperatures, suggesting that dissolution of M7C3 takes
place in the vicinity of M23C6 carbides only, and
supporting the above-mentioned mechanism.
When considering M2C carbides, a precipitate-free zone
was sometimes observed in the vicinity of M23C6 particles.
Dissolution of these M2C carbides releases molybdenum
into the matrix, however, the amount of molybdenum in
solid solution remains constant, at least at 948 K (675 C).
Thus, some of the released molybdenum probably diffuse
into M23C6 carbides, since their molybdenum content
remains constant during growth, and some of it may diffuse
toward other M2C particles, leading to their coarsening
and increasing their molybdenum content.
This evolution of carbide population during tempering
is in good agreement with the carbide precipitation
sequence from Baker & Nutting’s results and thermody-
namic equilibrium predictions for the considered holding
times and temperatures. M3C is the least stable carbide,
M7C3 and M2C are metastable and M23C6 is the equilib-
rium carbide. An increase in holding temperature accel-
erates the precipitation sequence, as metastable carbides
disappear more rapidly and M23C6 growth is favored.
B. Precipitation Sequence
From identification of individual precipitates, of their
location in the bainitic microstructure and their chemical
METALLURGICAL AND MATERIALS TRANSACTIONS A
composition, the overall carbide precipitation sequence in
the studied material can be considered as the result of several
precipitation sub-sequences. These sub-sequences seem to
occur simultaneously, in a rather independent manner for
shorter tempering times (or lower temperatures), and
interact with each other for longer tempering times and/or
higher tempering temperatures. For the particular granular
bainite starting microstructure and for the low heating rate
considered here, these can be described as follows:
 Retained austenite, located at the interfaces, decom-
poses into ferrite and M3C clusters during heating
and disappears before the temperature reaches
873 K (600 C), resulting in the microstructure
schematized in Figure 12(a). When heating up to
998 K (725 C), or during the isothermal step at
lower temperatures, cementite clusters then dissolve
due to nucleation and growth of M7C3 carbides at
the same location (Figure 12(b)).
 M2C carbides nucleate separately from the matrix
during the heating step, likely due to the carbon
atoms in solid solution or trapped at dislocations
within the bainitic laths (Figure 12(a)). Then, they
reach a maximum in their number fraction due to
both nucleation and growth (Figure 12(b)). For
longer times at 973 K and 998 K (700 C and
725 C), they start to dissolve due to their thermo-
dynamic instability.
 M23C6 carbides also nucleate separately but between
bainitic laths (Figure 12(a)) and quickly start to
grow, likely by extracting chromium atoms from the
solid solution (Figure 12(b)). For longer tempering
times, the growth of M23C6 leads to a continuous
dissolution of M7C3, and to coarsening of M2C
carbides (Figure 12(c)). For isothermal holding
times higher than a critical value, only M23C6
carbides remain in the material (Figure 12(d)). This
critical holding time is 24 hours at 998 K (725 C),
and longer at lower holding temperatures.
V. CONCLUSIONS
The four different carbides precipitating in the inves-
tigated fully bainitic 2.25 Cr-1 Mo steel with 0.15 wt pct
of C have been identified using literature data, experi-
mental measurements, and thermodynamic calculations.
Each type of carbide exhibits unique characteristics, such
as, the amount of metallic elements, morphology, crystal
structure, nucleation site, and nucleation conditions.
M3C cementite is the least stable carbide, M7C3 and
M2C are metastable carbides and M23C6 is the equilib-
rium carbide. No M6C was ever observed.
Precipitation of carbides starts during the heating
step, due to the low heating rate to be experienced by
thick-walled components. It is important to take this
step into account when considering the carbide precip-
itation, since all carbides have already precipitated
before the isothermal holding begins.
From experimental observations, the overall precip-
itation sequence was defined as the result of three
VOLUME 48A, MAY 2017—2177
precipitation sub-sequences that occur simultaneously.
Cementite (M3C) particles precipitate first due to the
decomposition of retained austenite. M7C3 carbides then
nucleate at the interface between cementite and matrix,
and grow by extracting both chromium and carbon
atoms from their parent M3C phase. Secondly, molyb-
denum carbides, M2C, precipitate homogeneously from
the matrix. Third, M23C6 particles precipitate, mostly at
interfaces but also at dislocations within the bainitic
laths. Finally, these three sub-sequences interact with
each other with increasing time and temperature, as the
growth of M23C6 induces the dissolution of neighboring
less stable M2C and M7C3 carbides.
ACKNOWLEDGMENTS
This work would not have been possible without
technical help of S. Gailliègue (MINES ParisTech), M.
Sennour (MINES ParisTech) and T. Guilbert (CEA
Saclay).
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