Journal of Nuclear Materials 602 (2024) 155359

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Journal of Nuclear Materials

journal homepage: www.elsevier.com/locate/jnucmat

Effect of prior microstructure on carbide precipitation in a Cr-Mo-V

pressure vessel steel at 650 ◦ C
K.V. Ravikanth a,b , Amit Verma a,b, J.B. Singh a,b,*, B. Vishwanadh a,c , S.K. Rai a,d ,
Malvika Karri a,b
a
Homi Bhabha National Institute, Anushakti Nagar, Mumbai, 400 094, India
b
Mechanical Metallurgy Division, Bhabha Atomic Research Centre, Mumbai, 400 085, India
c
Materials Science Division, Bhabha Atomic Research Centre, Mumbai, 400 085, India
d
Accelerator Physics and Synchrotrons Utilization Division, Raja Ramanna Centre for Advanced Technology, Indore 452013, India

H I G H L I G H T S

• Systematic experimental studies and thermo-kinetic simulations have been used to delineate the effect of prior microstructure on the carbide precipitation during
tempering of a Cr-Mo-V pressure vessel steel.
• Steel with two different initial microstructures, produced by cooling it at 10 ◦ C/min and water quenching from austenitization temperature, was investigated.
• Multiscale characterization revealed the presence of carbon-rich martensite/austenite (M/A) islands in the steel cooled at 10 ◦ C/min.
• M7C3 and MC carbides precipitated in both the samples during tempering at 650 ◦ C, while M23C6 carbide formed only in the 10 ◦ C/min cooled sample.
• Thermo-kinetics simulations showed that the carbon enrichment in the M/A constituents was responsible for the enhanced precipitation kinetics of M23C6 carbide.

A R T I C L E I N F O A B S T R A C T

Keywords: Cr-Mo-V steels are key materials used for constructing thick reactor pressure vessels (RPV) owing to an
Cr-Mo-V steel impressive combination of their mechanical properties and weldability. Conventionally, these steels are sub­
Martensite/Austenite jected to a quality heat treatment that comprises austenitization, quenching and tempering. Owing to its large
Tempering
thickness, an RPV experiences widely different cooling rates across its thickness during quenching, leading to
Carbides
Phase Stability
considerable variation in the microstructure from the surface to the centre of the vessel. In this study, a Cr-Mo-V
Thermo-kinetic simulations steel was austenitized at 950 ◦ C for 1 h and cooled at two rates (water quenching and 10 ◦ C/min), representative
of the cooling rates at the surface and centre of a typical RPV, to study the effect of prior microstructure on the
carbide precipitation during tempering of the steel at 650 ◦ C. Electron microscopy of the as-cooled samples
revealed the presence of martensitic microstructure in water quenched sample and predominantly granular
bainitic microstructure in slow cooled sample. Synchrotron studies revealed the presence of retained austenite
containing ~0.8% carbon in the slow-cooled sample. Tempering of the steel at 650 ◦ C for 200 h precipitated
M7C3 and MC (VC) carbides in the water-quenched sample, while the slow cooled samples precipitated M23C6 as
an additional constituent. This difference in the carbide precipitation in the two samples has been attributed to
the excess carbon in the martensite/austenite (M/A) regions in slow cooled samples and explained on the basis of
carbide precipitation sequence predicted using Thermo-kinetic simulations. This analysis has shown that M23C6
and M7C3 carbides in the slow cooled sample precipitate simultaneously as critical radii of their nucleation as
well as their incubation time become comparable when the matrix contains more than 0.25% C. The present
study has demonstrated that the microstructure prior to tempering may significantly affect the precipitation
sequence of carbides during tempering.

* Corresponding Author
E-mail address: [email protected] (J.B. Singh).

https://doi.org/10.1016/j.jnucmat.2024.155359
Received 1 July 2024; Received in revised form 21 August 2024; Accepted 22 August 2024
Available online 23 August 2024
0022-3115/© 2024 Elsevier B.V. All rights are reserved, including those for text and data mining, AI training, and similar technologies.
K.V. Ravikanth et al. Journal of Nuclear Materials 602 (2024) 155359

1. Introduction precipitation during subsequent tempering.

Carbide precipitation in Cr-Mo-V steels is a critical process that af­
Low alloy Cr-Mo-V (chromium-molybdenum-vanadium) steels are fects their mechanical properties, especially strength and toughness. The
extensively used in manufacturing pressure vessels for power generation common carbides that form in Cr-Mo-V steels include M23C6 and M7C3
and oil refining industries, owing to their superior durability in high- (typically rich in Cr, Fe), M2C and M6C (containing high Mo), MC
temperature environments and their resistance to oxidation and (typically V-rich), and Fe-rich M3C [14]. The affinity for carbon de­
hydrogen embrittlement. In a nuclear power plant (NPP), the reactor creases in the order V, Mo, Cr, Fe making MC carbides one of the most
pressure vessel (RPV) is an irreplaceable and life-limiting component, thermodynamically stable carbides [14]. However, the relative stability
typically designed for more than 50 years of operation under harsh of carbides in a given steel is quite sensitive to its composition. Different
conditions of neutron irradiation, high temperature, high pressure and research groups have investigated carbide precipitation sequences in
corrosion. The mechanical properties of the RPV should be adequate to low alloy Cr-Mo-V steels during their tempering as well as service under
maintain its structural integrity and reliability throughout the reactor’s varying conditions. For examples, Pigrova [15] analysed the carbide
operational life. A nuclear RPV is commonly fabricated from thick shells precipitation in four varieties of Cr-Mo-V steels containing 0.6-1.6Cr,
(~ 500 mm) of forged steel. The heat treatment cycle of thick RPV shells 0.3-1Mo and 0.3V during aging at temperatures between 450 and 700
typically comprises an austenitization treatment above 900 ◦ C followed ◦
C for times up 5000 hours. Pigrova [15] generalised the carbide pre­
by water quenching to room temperature, and a subsequent tempering cipitation sequence as: M3C → MC+M2C+M7C3 → MC+M2C+M23C6 →
treatment over a temperature range of 600 – 700 ◦ C to achieve the MC+M23C6+M6C. He has observed M2C carbides only in steels con­
desired combination of strength and toughness. taining relatively high Mo content and M6C carbides only after pro­
The cooling rates during quenching of the RPV shell vary typically longed service aging of the steels irrespective of their Mo concentration.
from about 4000 ◦ C/min at the surface to about 10 ◦ C/min at the centre As per Pigrova [15], M23C6 is more stable than M7C3 carbide in all the
of the shell [1]. This difference in the cooling rate may cause a variation steels. Wen et al. [16] have shown the formation of vanadium-rich
in the microstructure across the thickness of the RPV. The surface de­ MC-type carbide along with M2C carbide in Ni-Cr-Mo-V steels with
velops a finer microstructure due to the formation of martensite, which different vanadium contents. However, the M2C carbide forms only
increases its hardness and strength. On the other hand, the centre may when the V/Mo ratio in the steel is less than 0.23 [16].
develop a coarser microstructure comprising larger grains of allo­ Klueh and Swindeman [17] have investigated carbides in a Ti and B
triomorphic ferrite and pearlite due to the lower cooling rate experi­ modified 2.25Cr–1Mo-0.2V steel tempered at 690◦ C for 20 hours and
enced there. Allotriomorphic ferrite is detrimental to impact properties reported the formation of fine MC carbides, in addition to coarse M23C6
of RPV steel [2,3]. Therefore, the formation of the ferrite is minimised to and M7C3 carbides. Andrews et al. [18] have reported the formation of
avoid poor mechanical properties at the centre of the RPV. In between stable M6C and MC carbides in a 2.25Cr-1Mo-0.25V steel. Similarly,
the centre and the surface, a significant portion of the RPV predomi­ Miyata and Sawaragi [19] reported the formation of M(C,N) carboni­
nantly exhibits intermediate-scale bainite, whose morphology may also trides along with M7C3 and M23C6 carbides in a 2.25Cr–1Mo-0.25V steel
change substantially as a result of a large cooling rate variation. For tempered for 1 h at 770◦ C. However, Tsai et al. [20] have reported the
instance, the morphology of bainite in a Cr-Mo-V rotor steel varies from formation of metastable MC carbide along with stable M2C and M7C3
a mixture of lower bainite and upper bainite to granular bainite when carbides at 700◦ C after 200 h of tempering of a heat affected zone of a
the cooling rate from austenitization temperature decreases from 120 2.25Cr–1Mo-0.25V steel, because MC dissolved during further
◦
C/min to 5 ◦ C/min [4]. tempering. Similar metastable behaviour of MC has been reported by
The bainitic microstructure broadly comprises aggregates of ferrite Tao et al. [21] and Yongtao et al. [22] in 2.25Cr–1Mo-0.25V steel.
plates (sheaves) separated by secondary constituents like cementite, Akin to contrasting reports on the relative stability of MC and M2C
untransformed austenite, or a mixture of untransformed austenite and carbides, differences exist in literature on the relative stability of M23C6
martensite (often referred to as M/A constituent)[5]. Different classifi­ and M7C3 carbides in Cr-Mo-V steels. Many researchers [15,17,19,23]
cation schemes have been proposed to label the bainite microstructure have reported that M23C6 is a stable carbide that gradually replaces
depending on the nature and distribution of the secondary constituents M7C3 during the course of tempering or service aging, which is at
[5-8]. Among the proposed schemes, the one proposed by Zajac et al. [8] variance with observations by other researchers [20,24,25]. Janovec
is often followed. As per Zajac et al. [8], the bainite structure can be et al. [24] have identified equilibrium carbides in various low alloyed
categorized into five types: (1) upper bainite, which comprises lath-like Cr–V and Cr–Mo–V steels tempered between 500 and 720 ◦ C for up to
ferrite containing cementite particles at the lath boundaries; (2) 5000 h. They have observed stable M7C3 and MC carbides in all these
degenerated upper bainite, which consists of M/A constituents, instead steels at all temperatures, but M23C6 was also observed in steels
of cementite, on the ferrite lath boundaries; (3) lower bainite, which tempered at lower temperatures. They have found M23C6 metastable in
comprises lath-like ferrite containing intra-lath cementite particles, these steels and attributed its formation to the depletion of Cr and the
aligned at an angle to the long axis of the lath; (4) degenerated lower enrichment of Mo in the Fe matrix as a result of the prior precipitation of
bainite, which comprises lath-type ferrite and intra-lath M/A constitu­ M7C3 and MC carbides. Vyrostkova et al. [25] have also shown the
ents instead of cementite; (5) granular bainite, which comprises irreg­ formation of M23C6 in the limited temperature range between 497 and
ular ferrite grains with carbon-rich M/A constituents distributed in 578◦ C in low alloyed Cr–Mo–V steels. The absence of M23C6 carbide
between ferrite grains. Granular bainite is reported to form mostly in reported by Tsai et al [20] in a 2.25Cr–1Mo-0.25V steel tempered at
steels that are slowly cooled through the bainite transformation tem­ 700◦ C up to 500 h also supports metastable nature of M23C6 carbides.
perature regime [9,10]. The granular bainite is characterized by the Carbide precipitation sequence during tempering of Cr-Mo-V steels
formation of martensite/retained austenite (M/A) islands within a has also been shown to depend on their prior microstructure [15,26].
carbon-lean ferrite matrix. The slow cooling allows the diffusion of Pigrova [15] has shown that the precipitation of M23C6 in a
carbon away from ferrite regions to adjacent untransformed austenite. 1.6Cr-0.6Mo-0.3V steel is enhanced during tempering when the steel is
The untransformed austenite with higher carbon content may either subjected to air cooling, instead of water quenching, from the austeni­
remain stable or partially transform to martensite when cooled to room tization temperature. Parameswaran et al. [27] have shown that the
temperature, depending upon its carbon content, steel chemistry and time for the precipitation of M7C3 carbide in a 2.25Cr-1Mo steel reduces
cooling rate [5,11]. The carbon concentration in the M/A regions may appreciably when the steel is slowly cooled, compared to water
be as high as 10 times compared to the bulk carbon content of the steel quenching, from the austenitization temperature. These studies suggest
[11-13]. Such a high carbon concentration in localized regions in an that slower cooling from the austenitization temperature introduces
austenitized and quenched steel may significantly affect carbide some microstructure features that may alter the carbide precipitation

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K.V. Ravikanth et al. Journal of Nuclear Materials 602 (2024) 155359

sequence during subsequent tempering. Though the limited reports another set of samples were austenitized at 950◦ C for 1 h in a BAHR-
highlight the effect of prior microstructure on subsequent tempering, make quenching-deformation-dilatometer (model-805A/D) and subse­
they do not correlate the effect with the underlying microstructure. quently cooled at 10 ◦ C/min, henceforth referred to as Q2 samples
In summary, stability of carbides and their precipitation sequence throughout the text. The cooling rates for Q1 and Q2 samples were
during tempering of Cr-Mo-V steels still appear to be debatable. There is selected based on the steel CCT diagram (described later) to obtain
a need to address the issue through studies that can delineate the significantly different microstructure before tempering. Both Q1 and Q2
dependence of carbide stability and their precipitation sequence on steel samples were tempered at 650◦ C for 10, 50, 100 and 200 h duration in a
chemistry, prior microstructure and dynamically changing local chem­ Carbolite make tubular furnace. The samples were loaded in the furnace
ical composition of the matrix during tempering. In the present study, after it had reached 650 ◦ C, in order to avoid any possible effect of
the effect of prior microstructure on the evolution of carbides during heating rate on the tempering behaviour of the samples. A schematic of
tempering has been studied in a Cr-Mo-V steel. The steel with two sets of the heat treatment cycle is depicted in Fig. 1. The maximum tempering
microstructures, namely, (i) martensite, and (ii) granular bainite, pro­ time of 200 h was chosen to ensure sufficient period even for carbides
duced by cooling it at different rates from an austenitization tempera­ with very slow precipitation kinetics.
ture, was subjected to tempering at 650 ◦ C for different periods of time. Carbides in the tempered samples were selectively extracted from the
The tempering behaviour of the steel with two prior microstructural matrix using electrolytic extraction technique using a solution of 10%
conditions has been investigated using multiscale characterization tools HCl in methanol at a DC voltage of 1.5 V. During electrolytic extraction,
like Optical microscopy (OM), Scanning electron microscopy (SEM), the matrix was dissolved selectively leaving behind the undissolved
Transmission electron microscopy (TEM) and Synchrotron-X ray carbide particles, which were collected by centrifuging and drying.
diffraction (S-XRD) in conjunction with CALPHAD based thermo-
kinetics simulations to rationalize the difference in the precipitation 2.2. Continuous cooling transformations of the steel
behaviour of carbides on the basis of thermodynamic and kinetic factors.
This study has shown that slow cooling of the steel from the austeniti­ Hollow cylindrical specimens of length 10 mm, outer diameter 4 mm
zation temperature introduces retained austenite with significantly high and shell thickness 1 mm were used to obtain a continuous cooling
carbon concentration, which alters the relative stability of carbides transformation (CCT) diagram of the steel. All cooling experiments were
differently during subsequent tempering. carried out in the dilatometer under vacuum of a level better than
5×10− 4 mbar. Samples were austenitized at 950 ◦ C for 1 h and subse­
2. Material and Methods quently cooled using He spray gas to achieve controlled cooling rates
ranging from 3 ◦ C/min to 3600 ◦ C/min. The transformation tempera­
2.1. Material and Heat treatments tures during cooling were identified from inflection points in dilatation
curves.
An eastern grade Cr-Mo-V RPV steel, received in forged and
quenched and tempered (Q&T) condition, was studied in the present 2.3. Microhardness testing
work. The chemical composition of the steel, determined using Induc­
tively Coupled Plasma-Optical Emission Spectroscopy (ICP-OES), is Hardness of the as-quenched and quench-tempered specimens was
given in Table 1. Specimens for optical microscopy and SEM were pre­ measured using a Vickers hardness tester by applying a load of 300 gf for
pared following a standard metallographic preparation procedure a dwell time of 10 s. The measurements were performed on a polished
comprising mechanical grinding on successively finer sized SiC papers surface (final polishing done with 1 µm diamond paste) and ten hardness
up to 2400 grit, followed by polishing using a diamond suspension of 1 measurements were taken for each condition and the average hardness
µm. The specimens were etched with a 2% v/v Nital solution (2 ml HNO3 value is reported.
and 98 ml C2H5OH) for microstructural characterization. Electron
transparent samples for TEM characterization were prepared from thin 2.4. Microstructural characterization
strip of about 80-100 µm thickness, prepared by mechanical grinding
and polishing using abrasive SiC papers of upto 1000 grit size. Subse­ Microstructures of the quenched (Q) and quenched-tempered (QT)
quently, discs of 3 mm diameter were punched out from the thinned specimens were characterized using an optical microscope and a high-
strip and electron transparent disc foils were prepared in a Struers-make resolution Carl Zeiss make SIGMA field emission scanning electron mi­
Tenupol twin jet electropolishing machine using an electrolyte solution croscope. A JEOL make 3010 model transmission electron microscope,
containing 90% Methanol and 10% Perchloric acid maintained at -40◦ C operated at 300 kV, was used for TEM studies. The lattice parameters of
and an applied DC voltage of 20 V. the austenite and ferrite phases in Q2 sample were determined by
Prior austenite grain size (PAGS) of the steel was determined by Rietveld refinement of room temperature synchrotron X-ray diffraction
thermal etching it during an austenitization treatment at 950 ◦ C for 1 h data obtained at the Engineering Applications Beamline, BL-02 of Indus-
in vacuum. Prior to thermal etching, the sample was polished to mirror 2 synchrotron source in India. Synchrotron measurements were per­
finish. Subsequently, the thermally etched surface was examined in an formed in the high-resolution θ–2θ (reflection geometry) mode of the
optical microscope to determine PAGS using the linear intercept beamline, using a Huber diffractometer and PILATUS100 detector at a
method. wavelength λ ≅ 0.8265 Å. Whole-pattern decomposition (LeBail fitting)
The as-received steel was subjected to austenitizing treatment in of XRD data was performed using the FullProf software to calculate the
quartz ampules sealed under vacuum, which were immediately broken lattice parameters of the phases. A Bruker make D8 Discover X-ray
in a water bath to quench the samples at the end of each heat treatment. Diffractometer (XRD) equipped with Cu source and Lynxeye detector
After an austenitizing treatment at 950 ◦ C for 1 h, the water quenched was used for phase identification of carbides extracted from the
samples were sealed again in quartz tubes for the tempering treatments, tempered samples. High resolution XRD scans were performed using an
henceforth referred to as Q1 samples throughout the text. In addition, angular step size of 0.02◦ across 2θ-angular range of 30◦ to 90◦ . The

Table 1
Chemical composition of the steel (wt%)
Fe Cr Al Co Cu Mn Mo Nb Ni P Si Ti V C S

Bal. 2.75 0.03 0.11 0.06 0.42 0.61 0.02 0.67 0.04 0.27 0.02 0.24 0.17 81 ppm

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K.V. Ravikanth et al. Journal of Nuclear Materials 602 (2024) 155359

Fig. 1. Schematic drawing of the heat-treatment cycle

carbide phases were identified using the PCPDF database. allotriomorphic ferrite (α), bainite (αB), martensite (α′) or their mixture
depending on the cooling rate from austenitizing temperature. The
3. Results ‘onset’ and ‘finish’ temperatures of these transformations can be deter­
mined using a dilatometer from the inflection points in the dilatation
3.1. CCT diagram of the steel curve for the respective transformation.
A representative dilatation curve of the studied steel, cooled at 10
Fig. 2a shows an optical micrograph of thermally etched sample ◦
C/min from austenitization temperature to room temperature, is shown
revealing prior austenite grains in the sample austenitized at 950 ◦ C for in Fig. 2b. The steel had undergone two phase transformations, namely,
1 h. The analysis of optical micrographs, obtained from six different (i) austenite → ferrite, and (ii) austenite → bainite transformation during
regions of the sample, revealed the PAGS of the studied steel after the cooling. Fs, Bs and Bf refer to the ‘start’ temperature of the austenite →
austenitization treatment to be 70 ± 3 µm. In low alloy Cr-Mo-V steels, ferrite, ‘start’ temperature of the austenite → bainite and ‘finish’ tem­
austenite (γ) phase during cooling to room temperature transforms to perature of the austenite → bainite, respectively. The slope change at the

Fig. 2. (a) Optical micrograph showing prior austenite grains revealed by thermal etching. (b) Dilatometry curve of the studied steel for 10 ◦ C/min cooling rate
showing the austenite → ferrite transformation start temperature (Fs) and austenite → bainite transformation start (Bs) and finish (Bf) temperatures. Tt refers to an
‘end’ temperature of an incomplete transformation (see text for details). (c) CCT diagram of the studied Cr-Mo-V steel. Numbers in rectangular boxes refer to the
cooling rates (in ◦ C/min) employed for constructing the CCT diagram.

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K.V. Ravikanth et al. Journal of Nuclear Materials 602 (2024) 155359

temperature marked Tt appears to be the austenite → ferrite ‘finish’ water quenched low carbon steels.
temperature (Ff), but it is not as microscopy evidences (shown later) On the other hand, optical microstructure of the Q2 sample, shown in
revealed the presence of both ferrite and bainite at much lower tem­ Fig. 5a, was predominantly bainitic and contained sparsely distributed
peratures. This indicated that the austenite at the Tt temperature had not islands of allotriomorphic ferrite visible in the bright contrast (encircled
transformed completely into ferrite, else there would not have been any in the Fig. 5a). Fig. 5b shows a high magnification SEM image of a
bainite transformation at lower temperatures. Therefore, the Tt tem­ bainitic region, which comprised bainitic ferrite (dark regions) and
perature could not be called as the austenite → ferrite ‘finish’ (Ff) tem­ martensite/austenite (M/A) islands (slightly brighter contrast regions).
perature, which is consistent with the dilatation curve revealing Bs of the The M/A islands were further investigated using TEM. Fig. 6(a) shows a
austenite → bainite transformation that happens only from the un­ bright field TEM image of a granular bainite region comprising typical
transformed austenite phase. A similar uncertainty existed for identi­ M/A islands (dark contrast) along with bainitic ferrite (bright contrast).
fying the Ff transition temperature at other cooling rates, because of The two microstructure constituents were delineated by boundaries (in
which the CCT diagram was restricted to only the transformation start broken white lines). The bainitic ferrite contained a high density of
temperatures (Fig. 2c). The CCT diagram, shown in Fig. 2c, exhibited dislocations. The micro-diffraction patterns obtained from the M/A re­
two transformations of the steel during cooling: (i) one in the temper­ gion, marked by white and red circles, confirmed the presence of
ature range from 700-800 ◦ C which could be attributed to the formation austenite (Fig. 6b) and martensite (Fig. 6c) in M/A islands. A composite
of allotriomorphic ferrite; and (ii) the other at around 500 ◦ C, which selected area electron diffraction (SAED) pattern obtained from the M/A
corresponded to the bainitic transformation. The minimum cooling rate region containing both phases (marked by a white rectangle in Fig. 6a) is
required to prevent the formation of allotriomorphic ferrite in the final shown in Fig. 6d. The key to the SAED pattern, given in Fig. 6e, estab­
microstructure was found to be 40 ◦ C/min. lished that the austenite was oriented close to the [011] zone axis while
the martensite was oriented close to [001] axis, confirming that the two
3.2. Variation of micro-hardness with cooling rate and tempering phases in the M/A regions co-existed according to the well-known
duration Nishiyama-Wasserman crystallographic orientation relationship
({111}γ ‖{110}α and 〈110〉γ ‖〈001〉α ), which was consistent with litera­
Fig. 3 shows the effect of cooling rate on the hardness of the steel ture [28]. Further, the M/A regions appeared to be free of cementite, at
tempered for a given time. Evidently, the hardness of the water- least based on the SAED evidence, as Fig. 6d did not show the presence
quenched specimens after austenitization was significantly higher of any reflection corresponding to Fe3C.
(~480 HV) compared to ~375 HV of the sample cooled at 10 ◦ C/min. The martensite in M/A islands was internally twinned by {112}〈111〉
Upon tempering, the hardness of the samples decreased monotonically type twins (Fig. 7a), which was also consistent with the commonly
with time and reached a plateau after about 100 h. After 200 h of observed twinning in Fe-C martensite [29,30]. Fig. 7b shows a SAED
tempering, the hardness of both Q1 and Q2 samples reached nearly same pattern in a 〈113〉 zone axis from the twinned martensite shown in
values, indicating the two steels achieved nearly similar microstructure. Fig. 7a. Fig. 7b also showed faint reflections at 1/3{112} and 2/3{112}
positions, which Liu et al [29] have attributed to the presence of
3.3. Microstructure characterization metastable hexagonal ω-Fe phase at the twin boundaries in Fe-C
martensite. This type of twinned martensite is generally observed in
3.3.1. As-quenched specimens quenched high carbon steels containing more than 0.6% C [30].
Optical and secondary electron micrographs of the Q1 sample are Synchrotron study confirmed the presence of the retained austenite
shown in Fig. 4a and Fig. 4b respectively. Fig. 4a showed the presence of and ferrite phases in the Q2 sample (Fig. 8). The type of bainite observed
lath type martensite in Q1 microstructure. A high magnification in Q2 (Fig. 5 and Fig. 6) closely resembled granular bainite as per the
micrograph in Fig. 4b has clearly resolved the fine details of the typical classification given by Zajac et al. [8]. The granular bainite observed in
lath martensite structure by revealing the randomly oriented fine car­ the microstructure of Q2 is consistent with its formation in low-carbon
bides within some martensite laths. Carbide containing martensite steels subjected to continuous cooling after austenitization [10,23].
resembled auto-tempered martensite, which is commonly observed in Slow continuous cooling of the steel permits extensive transformation of
austenite to granular bainite during cooling to room temperature [5,10].
A characteristic feature of the granular bainite is the absence of carbides
in bainite sheafs. Due to the slow cooling rate, the supersaturated carbon
entrapped in the bainitic ferrite during the γ → γ + αB reaction diffuses
out to the surrounding austenite phase through γ/αB interface leaving
behind carbon lean bainitic (ferrite) sheafs. This results in the charac­
teristic feature of carbide free granular bainite, instead of carbide con­
taining bainite, during slow cooling. The carbon enrichment in the
neighbouring austenite stabilizes it even below the martensite start (Ms)
temperature (typically ~ 380 - 400◦ C) by suppressing the martensite
formation. Therefore, the final microstructure of such steels at room
temperature may contain both retained austenite and/or some high
carbon martensite/austenite (M/A) in addition to the bainitic ferrite. For
this reason, such granular bainitic microstructures contain islands of
M/A phase distributed homogeneously around bainitic ferrite sheafs.
The carbon enrichment in the austenite phase in Q2 sample was
confirmed from its lattice parameter value. The lattice parameters of the
ferrite and austenite phases were determined by Rietveld refinement of
the synchrotron data containing diffraction peaks corresponding to the
two phases in a constrained microstructural state. Fig. 8 also shows the
Rietveld fitted pattern to the measured diffraction pattern along with
their difference at the bottom of the figure. The goodness of the fit (GOF)
Fig. 3. Microhardness variation of the quenched samples (Q1 and Q2) with was evaluated on the basis of fitted parameters, termed R- and RF-
tempering time at 650 ◦ C.

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K.V. Ravikanth et al. Journal of Nuclear Materials 602 (2024) 155359

Fig. 4. Microstructure of the steel after water-quenching from austenitization temperature (Q1). (a) Optical micrograph showing lath martensite. (b) Secondary
electron image showing fine randomly oriented carbides inside the laths.

Fig. 5. Microstructure of the steel after cooling at 10 ◦ C/min from austenitization temperature (Q2). (a) Optical micrograph showing granular bainite and allo­
triomorphic ferrite (encircled in the image). (b) Secondary electron image showing martensite/austenite (M/A) islands (bright regions) in ferrite matrix.

factors. The Rietveld refined lattice parameters of the ferrite and designated as Q1T200 and Q2T200. Fig. 9 shows the microstructures of
austenite phases were 2.8737 Å (± 0.0002) and 3.6098 Å (± 0.0022), the two tempered samples exhibiting profuse precipitation of fine
respectively, and the corresponding R(Rf) factors for the two phases globular and elongated carbides at packet and block boundaries in both
were 0.0015(0.0061) and 0.0018(0.0024). Q1T200 and Q2T200 samples and relatively coarser carbides at prior
The carbon concentration in the retained austenite was estimated austenite grain boundaries (visible only in the field of view in Fig. 9a).
from the following well accepted Dyson and Holmes’ equation [31], Relatively coarser size of carbides at prior austenite grain boundaries
relating the austenite composition to its lattice parameter (aγ ) at room could be attributed to higher diffusivities of solutes along those
temperature. boundaries. The M/A islands observed in the Q2 sample (Fig. 5b) had
completely transformed into ferrite and carbides as a result of
aγ = 3.578 + 0.033wC + 0.022wN + 0.00095wMn + 0.0006wCr
tempering.
+ 0.0031wMo + 0.0018wV + 0.0051wNb + 0.0039wTi + 0.0018wW XRD analysis of carbide particles extracted from Q1T200 and
+ 0.0056wAl − 0.0002wNi − 0.0004wCo Q2T200 samples exhibited the presence of MC (cubic crystal structure)
and M7C3 (orthorhombic crystal structure) carbides in the Q1T200
sample, and M7C3 and M23C6 (cubic crystal structure) carbides in the
in which wi corresponds to the weight percent of element “i” in the
Q2T200 sample (Fig. 10). Similar observation of the M23C6 carbide in
austenite phase. Using this relationship, the carbon concentration of the
slow cooled Cr-Mo-V steel and its absence in water-quenched Cr-Mo-V
austenite phase with 3.6098 Å lattice parameter in the Q2 sample was
steel, that were tempered under identical conditions, have been reported
found to be about 0.8 wt%. The concentrations of all other solutes were
by Pigrova et al. [15]. It is interesting to note that XRD could not detect
taken from Table 1. 0.8% carbon in the austenite is significantly higher
the MC carbide in Q2T200 sample, even though MC is more stable than
than the 0.17% carbon content of the steel. This carbon enrichment in
M23C6 and M7C3 in such steels [14], and the same is predicted by
the austenite phase is consistent with the findings reported by Mohseni
thermodynamic simulations presented later. Therefore, the formation of
et al [13] and Wang et al. [12], who have shown that carbon content in
MC carbide even in Q2T200 sample could not be ruled out. The absence
retained austenite in a HSLA steel can be an order of magnitude higher
of discernible MC peaks in the Q2T200 XRD pattern could be attributed
than the nominal carbon concentration in the steel.
to the very low volume fraction of MC in the extracted particles.
3.3.2. Tempered specimens
The aim of the present work is to understand the effect of prior 4. Simulation of phase stability and precipitation sequence of
microstructure on the nature of carbide phases in tempered steels. This carbides
section presents microstructural details of Q1 and Q2 samples tempered
for 200 h, whose hardness had plateaued indicating that they achieved Experimental results have shown that there is an effect of the prior
nearly equilibrated microstructure. The two tempered samples are microstructure on the carbide phases formed during tempering. The
observed difference in the carbide phases in Q1T200 and Q2T200

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K.V. Ravikanth et al. Journal of Nuclear Materials 602 (2024) 155359

Fig. 6. (a) A bright-field TEM micrograph of a granular bainite region comprising typical M/A islands (marked by white broken lines) along with bainitic ferrite. (b)
and (c) micro-diffraction patterns from regions marked by white and red circles in (a) confirming the presence of retained austenite (b) and martensite (c),
respectively, in M/A islands. (d) shows a composite SAED pattern from the region marked by a white rectangle in (a) revealing the presence of both austenite and
martensite phases. (e) Key to the SAED pattern in (d). Individual SAD patterns corresponding to martensite (α’) and austenite (γ) are delineated by solid and broken
lines. Indexing of the individual patterns confirmed [001] and [011] as zone axes of the martensite and austenite phases, respectively.

Fig. 7. (a) Bright-field TEM image showing twinned sub-structure of the martensite in M/A islands. (b) A [131] zone axis SAED pattern of twins.

samples could be due to the presence of carbon rich martensite/ Table 1) were predicted by considering all the phases available in the
austenite (M/A) regions in Q2 sample. This difference had arisen due to database while performing the Gibbs free energy minimization. The
the variation in the cooling rates of the two samples from the austeni­ formation of metastable carbide phases during tempering of the steel
tization temperature. Thermodynamic stability of carbide phases and was predicted by suspending equilibrium carbide phases during calcu­
their likely precipitation sequence in the two samples (i.e., for nominal lations. The thermodynamic stability of different phases as a function of
carbon concentration in the Q1 sample and carbon-rich M/A regions in carbon content of the steel at 650 ◦ C was found out by plotting a
Q2 sample) were predicted using Thermo-Calc software [32] and property diagram, which shows their phase fraction variation with
accompanied TC-PRISMA package. The software package used TCFE11 carbon concentration of the steel. While varying the carbon content, the
database for thermodynamic computations and TCFE11 and MOBFE6 amounts of all other solutes were fixed as per the steel composition
databases for precipitation simulations. (Table 1) and the iron content was adjusted accordingly.
Fig. 11a and b show the stability of various phases in the steel as a
4.1. Thermodynamic stability of carbide phases function of temperature and as a function of carbon concentration at 650
◦
C, respectively. The dashed lines in Fig. 11a represent metastable
Equilibrium phases in the studied steel (composition given in phases, whose formation was predicted after suspending M23C6 carbide

7
K.V. Ravikanth et al. Journal of Nuclear Materials 602 (2024) 155359

with M23C6, M7C3, VC and Nb(Ti)C phases only when the steel contains
C > ~0.7%.

4.2. Precipitation sequence of carbides at 650 ◦ C

During tempering, carbides precipitate from martensite / bainite

matrix and the carbon rich retained austenite transforms to ferrite and
cementite [23,33]. In the present study, as the samples were loaded in
the furnace directly at 650 ◦ C for tempering, it was not unreasonable to
assume instantaneous decomposition of carbon enriched retained
austenite into ferrite and cementite. Therefore, precipitation of carbides
during tempering was considered to occur in the ferrite matrix. The
precipitation sequence of carbides in the ferrite matrix during tempering
at 650◦ C was simulated using TC-PRISMA software. A brief description
of the governing equations to model nucleation and growth of particles
in the TC-PRISMA software is presented below. More details of the
models can be found elsewhere [34]. Simulations assumed that pre­
cipitates are spherical and grow under a local equilibrium condition at
precipitate/matrix interfaces and ignored the diffusion of solutes within
Fig. 8. Synchrotron XRD pattern of the Q2 sample showing the presence of precipitates.
ferrite and retained austenite phases. Red curve shows the acquired pattern,
blue curve shows the fitted pattern and green curve shows the difference be­
tween the acquired and fitted pattern.

phase from the calculations. The steel exhibited M23C6, M7C3, VC and
(Nb,Ti)C equilibrium carbide phases in the temperature ranges of 200 -
750 ◦ C, 700 - 800 ◦ C, 200 - 900 ◦ C and 200 -1200 ◦ C, respectively. The
metastable carbides that can form in the temperature range of 200 - 700
◦
C were cementite (M3C), M6C and M2C. Further, the temperature sta­
bility range of M7C3 extended down to 250 ◦ C if the formation of M23C6
is suppressed, indicating that M7C3 formed as a metastable carbide in the
250-700 ◦ C temperature range. Irrespective of whether the calculations
considered M23C6 or not, the temperature stability ranges of VC and (Nb,
Ti)C phases remained unaffected, which suggested their higher stability
among the carbide phases in the steel studied. The calculations showed
that the thermodynamic stability of the carbides in the steel at 650 ◦ C
decreased in the order (Nb,Ti)C, VC, M23C6, M7C3, M2C, M6C, M3C. The
predicted thermodynamic stability of carbides is consistent with the
experimental results of the present study as well as with the experi­
mentally determined carbide stability in similar Cr-Mo-V steels reported
by Pigrova et al [15].
The stability of carbide phases as a function of carbon content at 650
◦
C is depicted in the form of a property diagram in Fig. 11b. At 650 ◦ C, a
steel containing carbon up to ~0.25% would form M23C6, VC and Nb(Ti)
C as stable carbides, while a steel having C > 0.25% would stabilize the
Fig. 10. XRD patterns of the carbides extracted from Q1T200 and
M7C3 phase also. The cementite phase would also become stable along
Q2T200 samples

Fig. 9. Secondary electron micrographs of the steel samples tempered for 200 h at 650 ◦ C. (a) Q1T200 (b) Q2T200

8
K.V. Ravikanth et al. Journal of Nuclear Materials 602 (2024) 155359

Fig. 11. Property diagram showing the variation of phase fraction (a) with temperature in the steel of composition given in Table 1, (b) with carbon content of the
steel at 650 ◦ C (concentration of all other solutes was fixed as per Table 1 and Fe concentration was adjusted accordingly during the calculation).

4.2.1. Nucleation model into consideration the extra nucleation sites available and the reduced
The nucleation of precipitates is modelled using the classical nucle­ interfacial energy due to defects like dislocations, grain boundaries,
ation theory (CNT) extended to multicomponent systems. According to grain edges etc. The value of the interfacial energy is estimated from the
CNT for binary systems, the transient nucleation rate J(t) is given by: thermodynamic data using a modified Becker’s model [36].
(− τ) ns zs
J(t) = Js exp (1) σ= ΔEs (6)
t NA z l

where Js is the steady state nucleation rate, τ and t are the incubation where ΔEs is the energy of solution in a multicomponent system, ns is the
time and reaction time, respectively. The steady state nucleation rate is number of bonds per unit area at the interface, zs is the number of bonds
expressed as per atom across the interface, zl is the coordination number of an atom
(
− ΔG∗
) within the bulk crystal lattice and NA is the Avogadro’s number.
Js = Zβ∗ N0 exp (2)
kT
4.2.2. Growth and coarsening models
where Z is the Zeldovich factor, β∗ is the rate of attachment of atoms or In the present work, growth and coarsening phenomena of carbides
molecules to the critical nucleus, N0 is the number of available nucle­ were simulated using the simplified model available in the TC-PRISMA
ation sites per unit volume, ΔG∗ is the Gibbs energy of formation of a module. The simplified model calculates the interface concentration by
critical nucleus, k is Boltzmann’s constant and T is the absolute tem­ choosing the tie-line across the bulk composition for modelling nucle­
perature. The Gibbs energy of precipitation of a second phase, β, from an ation, growth and coarsening of precipitates. The interfacial energy
α matrix, is given by between a carbide and the matrix was calculated from Eq. (6) using the
TCFE11 thermodynamic database.
16πσ3 The above model was used to simulate the precipitation kinetics of
ΔG∗ = ( )2 (3)
α→β M7C3 and M23C6 carbides, which distinguished the tempering behaviour
3 ΔGm
Vm
β of Q1 and Q2 samples. Initially, effect of carbon content in matrix
(martensite/bainite) on the precipitation kinetics of the two carbides
was studied at 650◦ C. At the outset, the three critical nucleation pa­
where ΔGαm→β is the maximum driving force for precipitation of β from α,
which is obtained by the parallel tangent construction in Thermo-Calc, σ rameters, namely, driving force (ΔGαm→β ), interfacial energy (σ ) and
critical radius (r∗ ) for the nucleation of M7C3 and M23C6 carbides were
is the interfacial energy and Vm
β
is the molar volume of β. For multi­
calculated. Table 2 provides the values of these parameters for different
component systems, Svoboda et al. [35] have defined the attachment
carbon concentrations in the matrix. Table 2 revealed that an increase in
rate β∗ as
the carbon content of the matrix from 0.17 to 0.4% increased the driving
( ⎡ )2 ⎤− 1 force for nucleation of both the carbides, though the increase was more
4πr ⎢ ∑n ∗2X β/α
i − X α/β
i ⎥ for M7C3. On the other hand, the interfacial energies of the two carbides
β∗ = 4 ⎣ ⎦ (4)
a i=1 Di Xi /β
α

Table 2
where a is lattice parameter of the matrix, Xi and Xi are the mole
β/α α/β
Effect of carbon content of matrix on the nucleation parameters of M7C3 and
fractions of an element i at the interface in the precipitate (β) and M23C6 carbides at 650◦ C
matrix (α), respectively, and Di is the diffusion coefficient of element i in Wt% C Driving force (J) Interfacial energy (J/ Critical radius (Å)
the matrix. The critical radius of a nucleus, r∗ , is given by m2)

− 2σVmβ M7C3 M23C6 M7C3 M23C6 M7C3 M23C6 Δr∗

r∗ = (5)
ΔGαm→β 0.17 -19352 -12624 0.387 0.336 3.459 4.352 0.89
0.25 -20109 -12898 0.381 0.303 3.274 3.845 0.57
The above CNT model assumes homogeneous nucleation and all the 0.3 -20393 -12958 0.375 0.285 3.179 3.593 0.41
equations remain same for heterogeneous nucleation also. However, the 0.35 -20588 -12969 0.368 0.269 3.089 3.387 0.30
input parameters N0 and σ change for heterogenous nucleation to take 0.40 -20718 -12943 0.360 0.255 3.003 3.218 0.22

9
K.V. Ravikanth et al. Journal of Nuclear Materials 602 (2024) 155359

decreased with increasing carbon of the matrix, but the decrease was sometime, M3C started dissolving while the volume fraction of M7C3
larger for the M23C6. These two factors contributed to a net reduction of continued to increase till a plateau, which coincided with complete
critical radii for the nucleation of both the carbides with increasing dissolution of M3C and the nucleation of M23C6. This precipitation
carbon content in the matrix. For a matrix with 0.17% carbon, the sequence can be summarised as
smaller critical radius of nucleation for M7C3 than M23C6 suggested a
MC→MC + M7 C3 + M3 C→MC + M7 C3 →MC + M7 C3 + M23 C6
higher likelihood of preferential precipitation of the former followed by
the latter. Further, the difference between the critical radii of M23C6 and The simulated precipitation sequence is broadly consistent with the
M7C3 (Δr∗ = rM ∗
23 C6
− rM
∗
7 C3
) reduced with increasing carbon concen­ precipitation sequences observed in similar steels [15,38,41] except for
tration in the matrix (see, e.g., Δr∗ ~0.9 Å at 0.17% C reduced to ~0.2 Å the precipitation of MC ahead of the M3C (cementite), which is reported
at 0.4% C), indicating that a higher carbon content in the matrix pro­ to precipitate first during tempering [40]. This discrepancy could
motes the simultaneous nucleation of the two carbides, instead of possibly be due to the ortho-equilibrium conditions assumed in the
preferential nucleation of M7C3 prior to M23C6. simulation for calculating the composition of carbide nuclei.
Based on the above findings, full scale simulations were performed Ortho-equilibrium conditions assume the composition of the nuclei with
for predicting the co-precipitation of M23C6 and M7C3 carbides along highest driving force, which is practically not true for cementite because
with other carbides (M3C and MC) during tempering of the steel at 650 cementite is known to precipitate under para-equilibrium conditions, in
◦
C. Though the presence of M3C carbide was not experimentally which the composition of the nucleus differs from the matrix only in
observed in the carbides extracted from the tempered samples, it was terms of the carbon content. Nonetheless, the precipitation sequence,
included in the simulations as M3C would have formed and dissolved particularly of M7C3 and M23C6 carbides, was consistent with the pre­
during the course of tempering at 650 ◦ C for 200 h. Such a transient cipitation observed in the Q1T200 sample (Fig. 10).
precipitation and re-dissolution of M3C during tempering of low alloy The effect of carbon content in M/A regions on the precipitation
steels have been widely reported [37-40]. The MC carbide in the sim­ sequence of carbides was studied by simulating carbide precipitation
ulations refers to VC carbide, as the austenitization temperature sequence as a function of carbon concentration in the precipitation
employed in the present study (950 ◦ C) is quite lower than the disso­ domain. Fig. 13 shows incubation period for the precipitation of 1×10− 9
lution temperature of (Nb,Ti)C (Fig. 11a). Hence, (Nb,Ti)C was not volume fraction of M3C, MC, M7C3 and M23C6 carbides as a function of
considered while performing the precipitation simulations of tempering matrix carbon content at 650 ◦ C. At 0.17% C, M23C6 carbide exhibited
at 650 ◦ C as it would remain undissolved in the matrix after austeniti­ largest incubation time among all carbides considered in the simulation
zation and quenching and, therefore, would not precipitate during and it reduced sharply with the increase of carbon content in the matrix
tempering. Other simulation parameters such as grain size, dislocation as evident in Fig. 13. The incubation period for all other carbides also
density, precipitate shape etc. were set to default values and elastic ef­ decreased with an increase in the matrix carbon content and plateaued
fects arising due to the precipitation of carbides in matrix were ignored. to nearly the same values at carbon concentrations above 0.25%. The
Generally, during precipitation simulations, the value of interfacial en­ predicted simultaneous precipitation of MC, M7C3 and M23C6 carbides in
ergy is taken from literature and adjusted to make the predicted kinetics carbon-rich M/A regions was consistent with their observation in the
of precipitation consistent with the experimental observations. In the Q2T200 sample (Fig. 10), and their precipitation sequence can be
present simulations, interfacial energy was calculated from the modified expressed as
Becker’s model as the aim of the simulation was to delineate the relative
M/A→α + M3 C + MC + M7 C3 + M23 C6 →α + MC + M7 C3 + M23 C6
effect of chemical composition on precipitation sequence of different
carbides. In the simulations, only grain boundaries were chosen as the It is interesting to note that the preferred order of precipitation in
nucleation sites for all the carbides, though independent simulations these steels is M3C, M2C, MC, M7C3, M23C6, though their thermodynamic
considering grain boundaries and dislocations for nucleation did not stability increases in the order M3C, M2C, M7C3, M23C6 and MC phases in
alter the simulation results significantly (data not shown). The compo­ the 500-650 ◦ C temperature range.
sition of the precipitation domain (matrix) was set to the full composi­
tion of the studied steel (Table 1).
Fig. 12 shows the change in volume fraction of carbides with time
during ageing of the steel with 0.17% C at 650 ◦ C. Fig. 12 depicts the
likely carbide precipitation sequence, in which MC formed first because
of its highest stability followed by the co-precipitation of M3C
(cementite) and M7C3 which coincided with the dissolution of MC. After

Fig. 13. Effect of carbon content of the matrix on incubation time of carbides
Fig. 12. Simulated volume fraction evolution of carbides during tempering of during tempering at 650 ◦ C predicted using TC-PRISMA. The volume fraction of
the steel of composition given in Table 1 at 650 ◦ C the carbides used to calculate their incubation time was 10− 9.

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K.V. Ravikanth et al. Journal of Nuclear Materials 602 (2024) 155359

5. Discussion and carbides during tempering (compare Fig. 5b with Fig. 9b). The na­
ture of carbides in the Q1T200 sample was different from those in
The multi-scale microstructural characterization and the CALPHAD Q2T200 sample, as evident from the Fig. 10. While M7C3 and MC (VC)
based thermo-kinetic simulations in the present study have together carbides were present in both the samples, M23C6 carbide was addi­
demonstrated that the rate of cooling from the austenitization temper­ tionally present in the Q2T200 sample. Even though the M3C could not
ature plays an important role in the microstructural evolution of a low- be observed in the present work, the phase stability diagram (Fig. 11a)
alloy Cr-Mo-V steel, which could significantly affect the carbide pre­ predicted its formation as a metastable phase at temperatures lower than
cipitation sequence during subsequent tempering. ~250 ◦ C, which transformed to M7C3 at higher temperatures. Therefore,
the formation of M3C in Q1T200 and Q2T200 samples during the early
5.1. Effect of cooling rate on the microstructure stages of tempering cannot be ruled out.

5.1.1. Before tempering

5.2. Carbide precipitation sequence during tempering
The above results have unambiguously demonstrated that the Cr-Mo-
V steel formed randomly oriented ferrite laths with a homogeneous
In Cr-Mo-V steels, different type of carbides like MC, M2C, M7C3,
distribution of fine carbides in the Q1 (water quenched) steel (Fig. 4).
M23C6, and M6C have been reported to form during accelerated ageing
The formation of fine carbides was attributed to auto-tempering of the
or during prolonged service [15,37,38]. The temperature regimes of
martensite during cooling, a phenomenon commonly reported in similar
existence of different carbides depend primarily on the chemistry of the
kind of steels [42]. This microstructure was devoid of any retained
steel. One or more metastable carbides are known to form during
austenite. On the other hand, the microstructure of the Q2 sample,
tempering before the formation of stable carbides. Several authors have
cooled at 10 ◦ C/min, was significantly different from that of the Q1
reported carbide transformation from MC→M2C, M3C→M7C3,
sample. The Q2 sample exhibited mainly granular bainite (Fig. 5a) along
M2C→M6C, and M23C6→M6C [37,44,45], which implied that acceler­
with sparsely distributed allotriomorphic ferrite in its microstructure.
ated ageing or prolonged service exposure could form one or more
The granular bainite comprised islands of martensite/retained austenite
carbides of the type MC, M2C, M23C6, M7C3, and M6C. Pigrova [15] has
(M/A) in a matrix of lath-type ferrite, unlike the typical upper/lower
reported that the carbide precipitation sequence in Cr(0.6-1.6)-Mo
bainite that comprises cementite in a matrix of lath-type ferrite (Fig. 5
(0.3-1)-V(0-0.3) steels, subjected to tempering in the temperature
and 6). The slow cooling of Q2 sample prevented the formation of
range of 500-800 ◦ C for up to 5000 h, can be broadly represented as M3C
intra-lath cementite by suppressing its nucleation (low driving force)
→ MC+M2C+M7C3 → MC+M2C+M23C6 → MC+M23C6+M6C. His study
and allowed the diffusion of carbon from the super-saturated bainitic
has shown that while M7C3 and M23C6 carbides precipitated in all the
ferrite to adjacent austenite. As the transformation proceeded, the
studied steels, MC formed only in vanadium containing steels and M2C
increased carbon concentration in the remaining austenite stabilized the
formed only in the steel containing 1% Mo. Baker and Nutting [38] have
austenite in that temperature range, which partially transformed to
also observed the formation of M2C in a 2.25Cr-1Mo steel during
martensite when cooled to room temperature leading to the formation of
tempering over a temperature range from 400 to 750◦ C for up to 10,000
M/A islands. The amount of martensite in the M/A islands depends upon
h and reported the carbide precipitation sequence in the steel as M3C →
the carbon and alloying content of the austenite as well as on the cooling
M2C+M3C → M7C3 → M23C6 → M6C. The studies of Pigrova [15] and
rate. The twinned martensite structure observed in an M-A constituent in
Baker and Nutting [38] have, thus, established that M2C and M6C car­
the present study (Fig. 7) is, therefore, a manifestation of its high carbon
bides form, along with MC, M7C3 and M23C6 carbides, in Cr-Mo-V steels
content, which resulted from carbon partitioning during bainite trans­
with a relatively high Mo content (~1%).
formation. Based on the S-XRD data, the carbon concentration in the
Though the carbide precipitation sequence during tempering of fully
austenite retained in the M/A regions was found to be about 0.8%,
martensitic low alloy steels is fairly well established [38-40], certain
which was significantly higher than that in ferrite (~0.02%). Such
differences have been reported in the precipitation sequence of carbides
higher carbon concentrations in M/A regions was consistent with the
during tempering of steels having different microstructures prior to
literature [11-13]. Thus, it was concluded that the microstructure of the
tempering [15,26,46]. Fig. 14 compares the incubation time for the
Q2 samples contained significantly carbon-rich austenite phase (in the
precipitation of different types of carbides in a 1.6Cr-0.6Mo-0.3V steel
M/A islands), compared to chemically more homogeneous Q1 samples,
[15]. Fig. 14 includes time-temperature-transformation (TTT) curves for
which would have affected the tempering response of the Q2 sample
(compared to that of Q1).

5.1.2. After Tempering

Upon tempering at 650 ◦ C, the hardness of the steel in two different
initial microstructural conditions (Q1 and Q2) decreased monotonously
with tempering time until a hardness plateau was attained after 200 h,
though the rate of decrease was higher for Q2 (Fig. 3). As the hardness of
both the samples had reached almost identical value (~ 200 HV) after
200 h of tempering, it was not unreasonable to construe that the two
samples had reached nearly a similar microstructural state. This was
consistent with experimental finding of similar arrangement of profuse
carbides at block and packet boundaries as well as at PAGBs in the
tempered microstructure (after 200 h) of both Q1 and Q2 samples
(Fig. 9). Although, the two microstructures also appeared similar in
terms of the size of carbide particles that formed at block and packet
boundaries of two samples, coarser carbides at the PAGBs in the
microstructure of Q1T200 sample were an exception. Coarser carbides Fig. 14. Time-Temperature-Precipitation diagram of carbides in a 1.6Cr-
at PAGBs were attributed to enhanced diffusivity of solutes along the 0.6Mo-0.3V steel subjected to two different cooling rates, water quenching
boundaries [43]. Further, the absence of M/A regions in the micro­ (WQ) and air cooling (AC), from austenitization temperature prior to tempering
structure of Q2T200 sample confirmed that the M/A regions in the [15]. The black dotted line indicates the limiting tempering time and temper­
microstructure of Q2 sample had completely transformed into ferrite ature for the existence of M3C.

11
K.V. Ravikanth et al. Journal of Nuclear Materials 602 (2024) 155359

carbides in the steel subjected to water quenching (WQ) and air cooling water-quenched steel, as the carbon potential of bainite in the air-cooled
(AC) from an austenitization temperature. The black dotted line in steel is increased due to the prior formation of pro-eutectoid ferrite. A
Fig. 14 indicates the limiting time and temperature for the existence of similar effect has also been reported by Zhang et al. [46] in a
M3C. It is evident from Fig. 14 that the precipitation of M7C3 would 2.25Cr-1Mo-0.25V steel, who have shown different carbide constituents
precede that of the M23C6 for both WQ as well as AC samples owing to in upper bainite (M7C3 + M23C6 + MC) compared to those that formed
the fact that smaller incubation time is required for the precipitation of in granular bainite as well as lower bainite
the former carbide. Further, Pigrova has also demonstrated that, in the (M7C3 + M23C6 + MC + M6C), after ageing the steel for 500 h at 700 ◦ C.
furnace cooled condition (slowest cooling rate), the steel forms stable In the present study, the only difference between the Q1 and Q2 samples
M23C6 prior to M7C3 when tempered under identical conditions. This was the different rates at which they were cooled from the austenitiza­
behaviour has been attributed to the opposite effect of the cooling rate tion temperature. This difference had induced a distinctive microstruc­
on the precipitation start curves of the two carbides - the M23C6 curve tural feature of carbon enrichment (Section 3.1.1.) in the M/A islands of
shifts to the left while the M7C3 curve shifts to the right such that the Q2 sample (Fig. 5b and Fig. 8). This carbon enrichment in the localized
M7C3 precipitation significantly lags behind M23C6 in the furnace cooled regions was mainly responsible for increased driving force for the pre­
sample [15]. The carbide precipitation sequence observed by Pigrova cipitation of carbides, as demonstrated by a reduction in the critical radii
[15] in 1.6Cr-0.6Mo-0.3V steel can, therefore, be summarized as of the M7C3 and M23C6 nuclei with increasing carbon in the matrix
(Table 2). This was also consistent with the kinetics simulations of
M3 C + MC→MC + M7 C3 →MC + M7 C3 + M23 C6 →MC + M23 C6 (7)
tempering at 650◦ C which showed that when the carbon content of the
Since the major carbide forming solutes (Mo and V) were present in a matrix was more than 0.25%, the critical radii of nucleation and incu­
similar concentration level in the studied steel, it was not unreasonable bation periods of the two carbides were comparable to promote simul­
to assume that the TTT diagram reported by Pigrova [15] would closely taneous precipitation of M7C3 and M23C6 carbides, instead of the
represent the precipitation behaviour of carbides in the present study sequential precipitation of M7C3 followed by M23C6, a common mech­
too. anism reported at lower carbon contents of the matrix. Therefore, it was
The microstructure of Q1T200 and Q2T200 samples can be described concluded that the M/A regions containing about 0.8% C were respon­
as sible for simultaneous nucleation of M23C6 and M7C3 carbides in
Q2T200 sample, unlike the case in Q1T200 sample.
(i) ferrite + MC + M7C3 for the Q1T200 sample;
(ii) ferrite + MC + M7C3 + M23C6 for the Q2T200 sample. 5.4. Practical relevance of the study

The observed carbide phases after tempering of the Q1 and Q2 The present study has revealed that the precipitation kinetics of
samples for 200 h at 650 ◦ C were consistent with their formation as per M23C6 during tempering of the studied steel is faster when it is slowly
the TTT diagram (Fig. 14) as well as the thermodynamic predictions cooled, rather than water quenched, from the austenitization tempera­
(Fig. 11a). The formation of M23C6 in the Q2 sample during tempering ture. This has been found to be due to carbon enriched M/A islands in
was therefore attributed to the shift of its precipitation start curve to­ the slow cooled samples, as a higher carbon content significantly ac­
wards lower time. The prior microstructure that formed during slow celerates the precipitation of M23C6 over M7C3 during tempering. The
cooling (10 ◦ C/min) of the sample from the austenitization temperature decomposition behaviour of M/A islands during tempering predicted in
was found to be pivotal in shifting the M23C6 precipitation curve, which this study is consistent with the findings of Jiang et al. [47], who have
is discussed in the next section. It was interesting to note from Fig. 11a shown that M/A islands in a normalized 2.25Cr-1Mo-0.25V steel
that a small volume fraction of M2C was expected, as a metastable car­ decompose into ferrite and clusters of coarse M23C6 carbides during
bide, during tempering at 650 ◦ C. However, XRD based phase analysis of tempering. However, faster M23C6 kinetics may also lead to the forma­
the carbides extracted from Q1T200 and Q2T200 samples revealed the tion of coarse M23C6 carbides in the microstructure of the tempered
absence of M2C in the tempered samples. This could be attributed either steel, which may be harmful for mechanical properties of the steel. The
to the transformation of M2C to a more stable phase with the progress of results of this study emphasize the need of a pre-tempering heat treat­
tempering or to the low volume fraction of M2C, which precluded its ment, often advised at lower temperatures for thick sections of such
detection using X-ray diffraction. This inference was in agreement with steels. A pre-tempering heat treatment would limit the growth and
Senior [14] who has reported that the volume fraction of M2C is coarsening of carbides during actual tempering by forming fine meta­
generally low in a 1Cr-1Mo-0.3V rotor steel tempered at 700 ◦ C for 24 h stable carbides, such as M3C, thereby providing more nucleation sites for
duration. Therefore, the carbide precipitation sequence in the studied the stable carbides.
steel can be expressed as
6. Conclusions
M3 C + MC→M2 C + MC + M3 C→MC + M7 C3 →MC + M23 C6 (8)
According to Eq.8, the carbides in the studied steel would form MC The effect of prior microstructure on carbide precipitation during
and M23C6 phases at 650◦ C. The absence of M23C6 in Q1T200 could be tempering of a Cr-Mo-V steel at 650 ◦ C has been investigated by sub­
attributed to delayed transformation of M7C3 to M23C6. The formation of jecting the steel to two different cooling rates (water quenching (Q1)
the M23C6 from the M7C3 was also consistent with predicted carbide and 10 ◦ C/min (Q2)) post austenitization treatment at 950 ◦ C for 1 h.
stability diagram (Fig. 11a) emphasizing the transient nature of the Key results of the present study are summarized below.
M7C3 phase.
1. The Cr-Mo-V steel subjected to water quenching (Q1) post auste­
5.3. Role of prior microstructure on enhanced precipitation kinetics of nitization formed a lath-type martensite containing fine intralath
M23C6 during tempering carbides. The microstructure was also characterized by the absence
of retained austenite. On the other hand, the microstructure of the
The above results have demonstrated that the precipitation of M23C6 steel cooled at 10 ◦ C/min (Q2) was significantly different from that
in Q2T200 sample was significantly accelerated in comparison to that in of the water quenched condition and predominantly comprised
the Q1T200 sample which did not form M23C6 carbide even after 200 h granular bainite along with sparsely distributed allotriomorphic
of tempering. Similar effect of prior microstructure has been reported by ferrite.
Parameswaran et al. [27], who have demonstrated that M7C3 carbide 2. The distinguishing microstructural difference between the Q1 and
precipitates more rapidly in air-cooled 2.25Cr-1Mo steel than in Q2 samples was the presence of carbon-rich martensite/retained

12
K.V. Ravikanth et al. Journal of Nuclear Materials 602 (2024) 155359

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