Materials Science & Engineering A 559 (2013) 486–495

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Materials Science & Engineering A

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

Microstructure, tensile and toughness properties after quenching

and partitioning treatments of a medium-carbon steel
E. Paravicini Bagliani a,n, M.J. Santofimia b,c, L. Zhao b,c, J. Sietsma b, E. Anelli a
a
Tenaris Dalmine R&D, Dalmine S.p.A., Piazza Caduti 6 luglio 1944 1, 24044 Dalmine, BG, Italy
b
Department of Materials Science and Engineering, Delft University of Technology, Mekelweg 2, 2628 CD Delft, The Netherlands
c
Materials Innovation Institute (M2i), Mekelweg 2, 2628 CD Delft, The Netherlands

a r t i c l e i n f o a b s t r a c t

Article history: The effect of different microstructures on the tensile and toughness properties of a low alloy medium
Received 19 March 2012 carbon steel (0.28C–1.4Si–0.67Mn–1.49Cr–0.56Mo wt%) was investigated, comparing the properties
Received in revised form obtained after the application of selected quenching and partitioning (Q&P) and quenching and
18 July 2012
tempering (Q&T) treatments. After Q&T the strength–toughness combination was the lowest, whereas
Accepted 25 August 2012
the best combination was achieved by Q&P, as a result of the carbon depletion of the martensite and the
Available online 1 September 2012
high stabilization of the austenite. Nonetheless, the presence of islands of martensite/austenite (MA)
Keywords: constituents after Q&P treatments prevented the achievement of toughness levels comparable to the
Quenching ones currently obtainable with other steels and heat treatments.
Partitioning
& 2012 Elsevier B.V. All rights reserved.
Tempering
Retained austenite
Bainite

1. Introduction
The quenching and partitioning (Q&P) process is a recently
proposed heat treatment to produce high strength steels with good
ductility, improving the mechanical properties that can be obtained
with other consolidated products based on transformation-induced-
plasticity (TRIP), dual phase or martensitic steels [1]. Q&P consists of
a partial or full austenitization, followed by an interrupted quench at
a quenching temperature (QT) between the martensite-start tem-
perature (Ms) and the martensite-finish temperature (Mf) to obtain a
predetermined combination of martensite and austenite. A partition-
ing stage at the same or at higher temperature (PT) allows carbon to
escape from the supersaturated martensitic phase into the untrans-
formed austenite in the absence of carbide precipitation. Thus,
austenite is stabilized and retained in the final cooling to room
temperature [2,3].This cycle aims at producing a microstructure of
carbon-depleted martensite and retained austenite, whose properties
offer advantages when high strength and good formability are
required, like in thin sheets for the automotive industry, as they
allow improvements in crashworthiness and weight reduction [4].
The design of products for structural, engineering, pressure or oil
and gas applications is based on the optimization of the strength and
toughness combinations at the minimum operating temperature.
These are decisive factors to prevent sudden and brittle failure and,
in pressure vessels, to promote a ‘‘leak before break’’ behavior.
n
Corresponding author. Tel.: þ39 0355602831; fax: þ39 0355602845.
E-mail address: epbagliani@tenaris.com (E. Paravicini Bagliani).
For these applications, when a yield strength (YS) greater than
1000 MPa is required, the current state-of-the-art commercially
available consists mainly of medium carbon quenched and tempered
(Q&T) steels, alloyed with elements such as chromium, molybdenum
and nickel. Grades with a minimum YS of 1140 MPa and good
toughness at  20 1C are available [5]. Medium-carbon carbide-free
bainitic steels also lead to yield strengths above 1000 MPa with 50%
fracture appearance transition temperature (FATT) of  20 1C or less
[6,7], although these steels in some cases require quite expensive
nickel alloying. In the case of carbide-free bainitic steels, the
toughness improvement is believed to be a consequence of the
suppression of the cementite precipitation by alloying the steel with
1.5 wt% silicon, which results in the retention of interlath films of
retained austenite in a matrix of upper bainite [8].
Steels resulting from the application of adequate Q&P routes are
formed by microstructures containing carbon-depleted martensite
and retained austenite, which have some morphological similarities
with the microstructures present in carbide-free bainitic steels.
However, little attention has been devoted to the combination of
yield strength and toughness achievable with this new class of
microstructures. Hong et al. [9] showed the possibility of reaching
higher yield strength and impact toughness by Q&P routes in
comparison with other traditional treatments, by studying the
behavior of a low carbon steel treated to reach the properties of
an X100 grade. Nonetheless, most of the research in Q&P steels has
been focused on strength and elongation analyses [1,3,10,11].
The object of the present work is to investigate the combina-
tions of strength and toughness reachable in a medium-carbon
steel alloyed with 1.5 wt% silicon, after the application of specially

0921-5093/$ - see front matter & 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.msea.2012.08.130
 E. Paravicini Bagliani et al. / Materials Science & Engineering A 559 (2013) 486–495
Table 1
Chemical composition of the high silicon steel (wt%).
C Si Mn Cr Mo Others
High Si 0.28 1.41 0.67 1.49 0.56 Ti, B, Nb, Ni
designed Q&P heat treatments. The relationship between micro-
structures and mechanical properties is analyzed and compared
with those obtained by treating the same steel according to Q&T
routes.
2. Experimental procedure
The chemical composition of the material used in this work is
shown in Table 1. The steel used for the investigation is a low
alloy medium carbon steel, originally designed to obtain carbide
free bainitic structures by continuous cooling cycles at yield
strength levels from 900 to 1200 MPa for structural and oil
country tubular goods applications. It was molten as ingot of
80 kg, reheated at 1200 1C and hot rolled in a pilot mill in sheets
of 6 mm thickness with a finish-rolling temperature around
1000 1C. Further heat treatments were applied to the steel by
dilatometry and by a salt bath setup.
The dilatometry study was conducted with a Bähr DIL 805
quenching dilatometer using quartz push-rods, and cylindrical
samples of 10 mm length and 4 mm diameter. The temperature
was monitored by a type-S thermocouple spot welded on the
surface of the specimen, the length being controlled by a LVDT.
The quenching gas was nitrogen. The dilatometry study was
carried out to determine (a) the critical temperatures, the critical
cooling rate leading to a fully martensitic microstructure and
the progress of the martensitic transformation, (b) the time–
transformation–temperature (TTT) diagram in the temperature
range between Ms and the bainite start temperature (Bs) and
(c) the effect of the quenching and partitioning parameters on the
stabilization of the retained austenite.
Small specimens of length  width  thickness 200  90 
5.5 mm3 were machined for the application of heat treatments in
the double salt bath configuration. A K-type thermocouple was
placed in a hole at mid-thickness to track the temperature variation
during the entire heat treatment. The procedure started with
austenitization in a furnace, followed by immersion of the sheet
in the first salt bath. This bath was set at a temperature of 3575 1C
lower than the QT, to reduce the time spent below Ms before
reaching QT. At QT point the cooling rate was typically 3–4 1C/s.
Right after reaching the QT, the specimens were transferred to the
second bath, set at 100 1C higher than the PT in order to speed up
the heating rate of the specimen. The sheet was removed from the
second bath at PT and held in air for 2 or 20 s, during which the
temperature of the specimen decreased by 5 and 40 1C, respec-
tively, before quenching in water to room temperature. Q&T
treatments were also carried out with the same steel by austeni-
tization, oil quench and tempering in a furnace for 30 min.
Microstructures were observed by scanning electron microscopy
(SEM) in a Zeiss EVO 50 microscope after standard mounting,
polishing and 2% Nital etching. Measurements of the austenite
grain size were carried out after the austenitization cycle, using a
Bechet–Beaujard etching, based on a picric acid solution and Teepol
[12]. The average austenitic grain size determined after quench was
(16.571.8) mm, expressed as mean linear intercept with 95%
confidence interval.
The presence of retained austenite in the microstructures was
studied by magnetic methods in a LakeShore 7307 Vibrating Sample
Magnetometer (VSM) for the case of dilatometric specimens and by
487
X-ray diffraction in a Bruker type D8-Advance diffractometer
equipped with a Bruker Vantec Position Sensitive Detector (PSD)
for the case of specimens treated in salt baths. The volume fraction of
retained austenite from both techniques was calculated according to
references [13,14]. The lattice parameter of the retained austenite
was determined by applying Cohen’s method to the austenite
reflections. From this measurement the carbon concentration in
austenite was calculated using the relationship [15]
ag ¼ 0:3556 þ 0:00453xC þ 0:000095xMn þ 0:00056xAl þ 0:0006xCr 20:0002xNi
where ag is the lattice parameter of the austenite in nanometers and
xC, xMn, xAl, xCr, xNi are the concentrations in weight percent of carbon,
manganese, aluminium, chromium and nickel, respectively.
Materials treated in the salt bath were machined after heat
treatment, to make the tensile and the Charpy V notch (CVN)
specimens. A layer of 0.3 mm was removed from the surface and
at this point no decarburization was present. The tensile test speci-
mens had a rectangular cross-section of 8  5 mm2 and a length of
the reduced section of 45 mm. The 0.2% offset criterion was used for
the determination of yield strength. The measurement of total
elongation after rupture (TE) depends on the specimen geometry
and on the distance between the gauge length marks. Following the
standard ISO 6892-1, proportional test pieces were used, with an
original gauge length of 5.65  OS0, where S0 is the initial specimen
cross-section. CVN tests were carried out with V-notch subsize
specimens of 10  5  55 mm3, at temperatures between 30 1C
and þ100 1C according to the standard EN 10045-1. The impact
energy was normalized to 10 mm according to the formula
KVnormalized ¼ KVtest 10 mm=5 mm. The fracture appearance was
visually evaluated.
3. Design and application of the heat treatments
3.1. Theoretical study of the steel
Before designing of the experiments, the selected steel was
studied on the basis of theoretical models available in the
literature.
One important requirement for the successful application of
Q&P treatments to a steel is the proper selection of the cooling
rate in the quenching step, in order to avoid phase transforma-
tions prior to the formation of martensite. The critical cooling rate
from full austenitization at 940 1C (selected for experiments as
explained in the following section) and with a grain size of
16.5 mm (experimentally determined) was calculated using the
commercial software JMatPro, obtaining 2 1C/s.
The optimum quenching temperature that gives the maximum
retained austenite content at room temperature at the end of a Q&P
cycle was also theoretically evaluated. This calculation required the
input of the carbon content of the steel, the Ms-temperature and the
progress of the martensitic transformation during cooling, these
latter being available from dilatometry curves. The calculations
followed the method proposed by Speer et al. [2], based on the
hypothesis of constrained carbon equilibrium (CCE), i.e. it is assumed
that only carbon can reach a uniform chemical potential in a
situation of immobile interface between austenite and martensite,
whereas iron and substitutional atoms cannot move. In order to
obtain retained austenite, the carbon enrichment must be sufficiently
high to decrease the relevant Ms below room temperature; a carbon
concentration around 1.3% is estimated to be necessary for this steel
[16]. The result of the calculation, reported in Fig. 1, shows that the
quenching temperature corresponding to the maximum of retained
austenite is 281 1C, with phase fractions of martensite and austenite
equal to 0.79 and 0.21, correspondingly.
488 E. Paravicini Bagliani et al. / Materials Science & Engineering A 559 (2013) 486–495
Fig. 1. Theoretical calculation of the retained austenite content as a function of
the quenching temperature.
Table 2
Critical temperatures (1C), obtained by
dilatometry (average of three tests).
Ac1 Ac3 Ms
771 75 896 710 358 74
Theoretical calculations were also performed to estimate the
partitioning time that ensures full carbon partitioning from the
martensite to the austenite at different partitioning temperatures.
The model presented by Santofimia et al. [17] was applied to a
Fe-0.28 1C system quenched at a temperature at which the
volume fraction of martensite formed is 0.77. A stationary
martensite–austenite interface and a total width of martensite
lath plus austenite film of 0.26 mm were assumed. This value was
based on the hypothesis of a typical width of the martensite laths
of 0.20 mm, constant during the martensitic transformation, and
of a width of the austenite films of 0.06 mm, dependent on the
austenite fraction present at QT [17]. Three partitioning tempera-
tures, later selected in the experimental study, were considered in
the calculations—420 1C, 470 1C and 500 1C. The minimum parti-
tioning time needed for full carbon partitioning from martensite
to austenite in such conditions is 3 s, 0.4 s and 0.2 s, respectively.
3.2. Experimental study of the steel
On the basis of the theoretical analyses, a preliminary dilato-
metry study of the steel was carried out to identify the conditions
that stabilize the retained austenite in Q&P treatments.
The critical temperatures Ac1 and Ac3, listed in Table 2, were
determined by heating a cylindrical specimen of 10 mm length
and 4 mm diameter, according to ASTM A 1033, at 28 1C/h above
650 1C. On the basis of this result, an austenitizing condition
above Ac3 of 940 1C for 10 min was chosen for the design of Q&P
and Q&T treatments.
Continuous-cooling tests were carried out after full austenitization
to experimentally determine the Ms-temperature and the critical
cooling rate that gives 100% martensite. As shown in Fig. 2, the
dilatometric curve at 2 1C/s did not reveal traces of phase transforma-
tions above Ms, whereas the curve at 1 1C/s displayed the formation
of bainite. The rate of 2 1C/s was identified as the minimum rate
to have a fully martensitic structure, as was previously predicted
from the calculations with JMatPro. The experimental value of the
Ms-temperature is given in Table 2.
After the interrupted quench at QT the untransformed austenite
must undergo the partitioning stage. During this step, the decom-
position of the residual austenite into new phases is undesired,
Fig. 2. Dilatometric plots of continuous cooling tests at 1 1C/s and 2 1C/s.
because these phenomena would overlap and compete with the
process of carbon partitioning. This requires the selection of
appropriate partitioning temperatures at which new phases such
as bainite do not form. With this aim, the possible formation of
phases during isothermal treatments after full austenitization
above the Ms-temperature was experimentally investigated.
The TTT diagram, determined starting from a fully austenitic
structure was carried out to identify possible ranges of tempera-
ture where the austenite does not transform into bainite or ferrite
that could be exploited to avoid phase transformations during
partitioning. Results of such investigation can be used as a guide;
however it is important to note that these results may slightly
differ from the case of isothermal transformations at the same
temperatures after partial quench below Ms, since the presence of
martensite may affect nucleation, grain size and internal stresses
of the new forming phase [17–19].
The isothermal treatments were carried out by the dilatometer
at temperatures between 370 1C and 500 1C and the results are
shown in Fig. 3a. The ‘‘finish’’ curve indicates the end of the phase
transformation according to dilatometry, but this does not imply
the complete transformation of the austenite [20]. Above 470 1C,
and at least up to 500 1C, the steel is characterized by a range of
temperatures, close to the Bs temperature, where the austenite is
stable for very long times, whereas an increasing amount of
bainite is formed when the isothermal temperature is decreased
towards Ms. An example of microstructure, obtained after iso-
thermal treatment at 400 1C, is shown in Fig. 3b. It is mainly
composed of fine plates of bainite with films of retained austenite,
although coarse blocks of high-carbon martensite plus retained
austenite (MA-constituent) can also be observed. This constituent
was also present after isothermal treatments at lower tempera-
tures and it is related to an incomplete transformation of bainite
controlled by the T0 0 line, at which the bainite and ferrite have the
same free energy [20].
3.3. Design of Q&P treatments
The Q&P routes designed in this work followed the sequence
displayed in Fig. 4. The considered criteria for the design of heat
treatments are listed below:
(a) Complete austenitization above the Ac3 temperature;
(b) cooling rate fast enough to avoid any phase transformations
before martensite formation;
(c) interrupted quench at the temperature QT between Ms and Mf;
(d) short holding time at QT but long enough to ensure the thermal
homogenization of the specimen;
 E. Paravicini Bagliani et al. / Materials Science & Engineering A 559 (2013) 486–495 489

Table 3
Details of the Q&P cycles carried out by the dilatometer.

Austenitization Cooling QT (1C) Reheating PT Pt (s)

rate (1C/s) rate (1C/s) (1C)

940 1C for 50 260; 285; 20 420 100

10 min 300; 325 470 10, 60, 600
500 30, 600

Table 4
Austenitization, quenching and partitioning temperatures (TAust, QT and PT,
respectively) and austenitization and partitioning times (tAust, Pt) applied with
a salt bath setup. Pt ¼tempering time for QT500 and QT550.

Name TAust (1C) tAust (s) QT (1C) PT (1C) Pt (s)

QP243 970 50 243 515 20

QP253 952 400 253 511 20
QP263 929 480 263 511 20
QP276 954 580 276 504 2
QP281 941 420 281 513 20
QP291 934 800 291 500 2
QP314 949 650 314 518 2
QP-B 959 320 288 418 100
QT500 940 600 20 500 1800
QT550 940 600 20 550 1800

above and below the estimated optimum quench temperature.

Fig. 3. (a) TTT diagram between Ms and Bs of the material under testing.
Partitioning temperatures equal to 470 1C and 500 1C were con-
A: austenite, B: bainite. The cooling rate from austenitizing T to holding T was sidered in order to define a feasible working window for the salt
50 1C/s and (b) microstructure of the specimen treated isothermally at 400 1C. bath treatments. At these temperatures the precipitation of cemen-
tite cannot be excluded. Experimental observations after holding at
450–500 1C of various steels with high silicon contents [21], and
theoretical calculations [22] suggest that the precipitation kinetics
a) is slow compared with that of the process of carbon partitioning,
providing a working window for the carbon enrichment of the
austenite. Partitioning at temperatures lower than 470 1C increases
b)
the probability to form bainite, but as far as this constituent is
Temperature

Pt carbide free, it contributes to the stabilization of the austenite. For

PT
f) this reason a partitioning temperature of 420 1C was also selected.

e)
3.3.2. Salt baths
g)
c) QT The Q&P routes for salt bath experiments were chosen on the
d)
basis of the results obtained with the dilatometer. The heat
treatments were carried out with slight differences between real
and target temperatures. The indicative values of austenitization,
quenching and partitioning temperatures recorded with a ther-
time
mocouple and the corresponding times are displayed in Table 4.
Fig. 4. Scheme of the Q&P cycles. The quenching temperatures were between 240 1C and 315 1C in
order to obtain different fractions of austenite and martensite.
The partitioning stage was carried out reheating to 500 1C
(e) reheating of the specimen to the partitioning temperature PT, (above Bs), cooling in air down to approximately 470 1C and
at a reasonably fast rate to minimize the concurrence of quenching in water. In three cases the piece was immediately
processes, but not too far from industrially feasible rates; quenched in water after reheating in the second bath. One Q&P
(f) adequate partitioning temperatures and times (Pt), in which treatment was applied with quenching to approximately 290 1C
the formation of bainite is avoided and the homogenization of and partitioning at a temperature of about 420 1C corresponding
carbon within the austenite is complete; and to bainite formation after full austenitization. This specimen
(g) final quenching to room temperature. was identified as QP-B. In addition, two Q&T treatments with
tempering at 500 1C and 550 1C were applied.
In the following, the selected Q&P treatments for dilatometry
and salt bath experiments are described. 4. Results and discussion

4.1. Dilatometry study

3.3.1. Dilatometry
Table 3 shows the details of the Q&P cycles performed by the 4.1.1. Partitioning at 470 1C and 500 1C
dilatometer. The effect of QT on the stabilization of the retained Fig. 5 shows the measurements of retained austenite as a
austenite was determined by exploring a range of temperatures function of QT, with PT¼470 1C and 500 1C and holding times
490 E. Paravicini Bagliani et al. / Materials Science & Engineering A 559 (2013) 486–495
between 10 s and 600 s. The theoretical values of Fig. 1 are also
reported. The effect of QT can be observed in the tests carried out
with partitioning at 470 1C for 60 s. Considerable amounts of
retained austenite were obtained (0.12–0.18) stopping the
quench between 260 1C and 325 1C. The maximum of 0.18 was
reached between 285 1C and 300 1C. The maximum retained
austenite and the optimum temperature are quite in agreement
with the predictions, whereas at higher QT the experimental
retained austenite values are higher than the predicted ones.
Differences between experiments and calculations can be caused
by the fact that the applied model does not consider the kinetics
of carbon partitioning [17].
During partitioning, the dilatometric curves do not show
evidence of phase transformations, which would have been
revealed by an expansion of the specimen. This is in agreement
with the information provided by the TTT (Fig. 3a) regarding the
stability of the austenite in this range of temperatures.
Fig. 5. Retained austenite contents for various QT, after partitioning at 470 1C and
500 1C. The arrows indicate the trends with increasing partitioning times. The dot-
dashed line reproduces the calculated values of Fig. 1.
Fig. 6. Microstructures partitioned at 470 1C for 60 s after quenching to (a) 260 1C (volume fraction of retained austenite ¼0.14), (b) 325 1C (volume fraction of retained
austenite¼ 0.12) and (c) microstructure partitioned at 500 1C for 600 s after quenching to 300 1C (retained austenite fraction 0.11). RA: retained austenite, TM: tempered
martensite and UM: untempered martensite.
The effect of partitioning time at 470 1C is shown by the tests
with holding times of 10 s, 60 s and 600 s after quench to 300 1C.
After 10 s, the process of carbon partitioning was not completed
as the maximum content of austenite was not reached. Note that
the remarkable stability of the process was up to 600 s. The
predicted partitioning times at 470 1C (Section 3.1) were less than
1 s, in the assumption of martensite lath plus austenite film of
0.26 mm. This would indicate that longer diffusion paths of carbon
must be taken into account to achieve a homogeneous stabiliza-
tion of the austenite.
After partitioning at 500 1C for 30 s, the volume fractions of
retained austenite were slightly lower than those obtained at
470 1C for 60 s with the same quenching temperatures; moreover,
a considerable decrease of the retained austenite content was
observed for longer holding times. A possible explanation for
this observation is the starting of carbide precipitation, although
further analyses with TEM would be necessary to confirm this
point.
The final microstructure of the specimen quenched to 260 1C,
which is about 30 1C below the optimum quench temperature,
and partitioned at 470 1C for 60 s, is shown in Fig. 6a. It is possible
to observe the carbon-depleted martensite laths, with some
carbides inside. Their presence was likely due to a slight auto-
tempering of the martensite before the partitioning, as they
were also observed in tests with a partitioning time of 1 s. No
quantitative measurements of carbides density were carried out,
hence a further precipitation during partitioning cannot be
excluded. The unetched areas can be either retained austenite
(RA) or untempered high carbon martensite (UM). The fraction of
these areas is greater than the fraction of retained austenite
measured by the magnetic technique, therefore some high-
carbon martensite formed during the last quench appears to be
present.
The insufficient carbon enrichment of the austenite that comes
from quenching above the optimum temperature can be observed
in Fig. 6b, which shows the presence of coarse islands of untem-
pered martensite (UM). When the QT of 325 1C was reached, the
 E. Paravicini Bagliani et al. / Materials Science & Engineering A 559 (2013) 486–495 491

dilatometric curve indicated that the volume fraction of phases in

the microstructure consisted approximately 0.50 martensite and
0.50 austenite. In the final microstructure the volume fraction of
retained austenite was 0.12, therefore a volume fraction of UM of
0.38 could have formed during quenching from PT.
In the case of partitioning at 500 1C for 30 s and 600 s, the
microstructures do not show significant differences at SEM exam-
ination. They confirm the presence of islands of high-carbon
martensite, in particular in the specimen held for 600 s (Fig. 6c).
On the basis of these tests, a feasible working window to
obtain a microstructure of tempered martensite and austenite
was defined, which was an essential step for the design of the salt
bath treatments. In summary, during partitioning at temperatures
greater than or equal to 470 1C no phase transformations were
observed in the dilatometric curves, thus achieving the thermal
stabilization of considerable amounts of austenite by carbon parti-
tioning from martensite. Nevertheless, while the temperature of
470 1C could be maintained for quite long time (600 s) without
reducing the stability of the austenite, at 500 1C this was possible
only with short holding times. For the subsequent heat treatments
in salt bath, partitioning between 470 1C and 500 1C for 20–30 s was
considered to be adequate to obtain the desired microstructure.

4.1.2. Partitioning below the Bs temperature

The volume fractions of retained austenite measured after
partitioning at 420 1C for 100 s are shown in Fig. 7. When the QT
was 300 1C, close to the optimum quench temperature, the auste-
nite fraction was a bit lower than that obtained after partitioning
above Bs. On the other hand, with QT¼325 1C, which is about 40 1C
above the optimum quench temperature, a higher stabilization of
the austenite was obtained after partitioning below Bs.
In order to understand these results, dilatometric curves corre-
sponding to the change in length recorded during partitioning at
420 1C in the specimens previously quenched to 300 and 325 1C are
presented in Fig. 8a. Both specimens show an isothermal expansion
proportional to the amount of untransformed austenite at QT: the
specimen quenched to 325 1C had an initial fraction of austenite of
0.50, and shows an expansion of 0.11% whereas the specimen
quenched to 300 1C, with a fraction of austenite of 0.30, shows an
expansion of 0.036%.
Fig. 8b shows the microstructure of the specimen quenched to
325 1C and partitioned at 420 1C for 100 s. Comparing this micro-
structure with that obtained after quenching to the same tem-
perature and partitioning at 470 1C for 60 s (Fig. 6b), it is clear
that the latter showed coarse islands of austenite transformed
into martensite during the final quench that are not observed in
Fig. 8. (a) Dilatometry curves during partitioning at 420 1C, after quench to 325 1C
and to 300 1C and (b) microstructure after interrupted quench at 325 1C and
partitioning at 420 1C for 100 s. Volume fraction of retained austenite 0.17.
RA: retained austenite, MA: high carbon martensite-retained austenite constituent
and UB: upper bainite.
the specimen partitioned at 420 1C. On the contrary, this speci-
men exhibits regions of ferrite free carbides surrounded by small
islands of retained austenite or UM.
The expansion measured by dilatometry at 420 1C can be
explained either by an isothermal growth of martensite either
by the formation of bainite at the expenses of the untransformed
austenite. The microstructural features observed in the specimen
partitioned at 420 1C suggest the formation of bainite, which
probably contributes to an additional carbon enrichment of the
austenite and thus increasing its thermal stabilization with
respect to partitioning above the Bs temperature. If it is bainite,
the transformation occurs without incubation time, which indi-
cates an acceleration of the formation of bainite with respect to
the bainite kinetics observed from full austenitization at the same
temperature.

4.2. Heat treated sheets—microstructures

The volume fraction and carbon content of retained austenite in

Fig. 7. Volume fractions of retained austenite obtained after quenching to 300 1C
and 325 1C and partitioning at 420 1C for 100 s (open triangles), compared with an
isothermal treatment at 400 1C (solid triangle). The dotted curve represents the
measurements after partitioning at 470 1C for 60 s (Fig. 5).
specimens treated with the salt bath setup are reported in Fig. 9 as
a function of the QT. Except for the case of the treatment with the
highest quenching temperature (QT¼315 1C), in which the volume
fraction of retained austenite was 0.08, the retained austenite
fraction is between 0.10 and 0.13. The maximum is reached with
QT¼ 252–260 1C and the maximum carbon enrichment is achieved
with QT¼242 1C. No significant differences were found between
the specimens that underwent a partitioning of 2 s (QP276 and
QP291) and the ones partitioned for 20 s after quench to similar
temperatures (QP264 and QP281). In both cases the partitioning
time, summed to the time spent during the reheating from QT to PT
(about 20 s), was long enough to achieve similar results in terms of
492 E. Paravicini Bagliani et al. / Materials Science & Engineering A 559 (2013) 486–495

austenite stabilization. The retained austenite content of QP-B was
in line with the Q&P samples and its average carbon concentration
was a bit higher. After the Q&T heat treatments no retained
austenite was detected.
The retained austenite fractions measured in salt bath speci-
mens were generally lower and less sensitive to QT variations
than those measured in the dilatometric specimens. The peak
corresponding to the maximum in the volume fraction of retained
austenite was shifted to lower quenching temperatures in the
case of the specimens treated with salt bath (250 1C instead of
280 1C). These differences can be due to a less accurate control
of the thermal parameters during the application of the heat
treatments in salt bath, with respect to the better-controlled
temperature profile in the dilatometer. In order to clarify this
aspect, microstructures of some selected specimens treated in the
salt baths are displayed in Fig. 10. Two types of constituents can
be observed after Q&P treatments in the salt bath:

(a) Etched lath structures, corresponding to martensite laths that

Fig. 9. Retained austenite and untempered martensite fractions and carbon content
in retained austenite after salt bath treatments as a function of the quenching
temperature (QP specimens¼ open symbols, QP-B specimen: solid symbols).
underwent carbon partitioning to the austenite. In some cases,
these laths show carbide precipitation, also in the specimens
that underwent a partitioning stage of 2 s. They were mainly
caused by the autotempering of this martensite (TM) during the
time between quenching (salt bath 1) and partitioning (salt
bath 2) stages (Fig. 10a). Occasionally, islands of lower bainite
(LB) can be observed (Fig. 10b). In the first salt bath the cooling
rate between the austenitization temperature and Ms was
about 60 1C/s, well above the critical cooling rate, and no phase
transformations are expected. Below Ms the cooling and heat-
ing rates were lower than in the dilatometer due to the reduced
difference in temperature between piece and salt bath. This
caused a more extended autotempering of the martensite
formed in the first quench and the formation of small amounts

Fig. 10. Scanning electron micrographs of the following specimens: (a,b) QP252; (c) QP243; (d,e) QP263 and (f) QT550 (550 1C). RA: retained austenite, MA: high carbon
martensite-retained austenite constituent, TM: tempered martensite, UM: untempered martensite, LB: lower bainite.
 E. Paravicini Bagliani et al. / Materials Science & Engineering A 559 (2013) 486–495 493

of lower bainite, affecting the fractions of retained austenite

finally obtained in the specimens.
(b) Unetched laths and islands showing a smooth surface, which
correspond to retained austenite or to martensite formed in
the last quench of the Q&P process (MA-constituents) Since
the fraction of the unetched areas is higher than the retained
austenite fraction measured by XRD, some of these islands
correspond to untempered martensite, also at the lowest QT.
Neglecting the small amounts of lower bainite, the fraction of
UM in the Q&P specimens can be estimated as the balance of
the fraction of martensite formed during the first quench,
which can be derived from the dilatometry curve, and the
fraction of retained austenite measured by XRD. The specimen
with QT¼315 1C has a fraction of UM of 0.35. When QT is
reduced from 290 1C to 240 1C the content of UM decreases
from 0.15 to almost 0. These values are reported in Fig. 9.

Although at the lowest quench temperatures (240–250 1C) the

estimated fraction of untempered martensite is very low, this
constituent can be clearly observed around the areas of more
intense precipitation (Fig. 10a and b). Nonetheless, blocky struc-
tures can also be observed in regions where the formation of
carbides is not evident. They can be small islands of austenite that
remained untransformed and did not receive enough carbon from
the surrounding martensite to be stabilized, leading to the forma-
tion of UM or MA-constituent in the final quench (Fig. 10c–e).
After Q&T treatments the microstructure is tempered marten-
site with an extended precipitation of carbides, mainly present as
coarse films between the laths and blocks of martensite (Fig. 10f).
Fig. 11. (a) YS, UTS and TE of Q&P (open symbols) and QP-B (solid symbols)
4.3. Heat treated sheets—mechanical properties and influence materials and (b)YS and YS/UTS ratio versus UM fraction of Q&P specimens.

of the microstructure
Table 5
4.3.1. Tensile properties Tensile properties and 50% fracture appearance transition temperature (FATT) of
Fig. 11a shows the yield strength, ultimate tensile strength (UTS) QT500, QT550, QP243 and QP253 specimens.
and total elongation (TE) versus the quenching temperature of the
ID YS (MPa) UTS (MPa) TE (%) 50% FATT (1C)
specimens treated following Q&P schedules with the salt bath. The
steels exhibited almost constant UTS between 1450 and 1500 MPa, QT500 1194 7 12 1415 7 7 14.0 7 0.5 4100
except for the case with the highest quenching temperature, with QT550 1141 7 0 1300 7 0 13.8 7 0 68
UTS¼1600 MPa, where the presence of untempered martensite QP243 1170 7 0 1505 7 5 13.7 7 0 13
was significant. The YS values were between 800 and 1175 MPa and QP253 1175 7 15 1457 7 5 14.4 7 0.3 10

the TE values were between 8% and 14.5%, both increasing to a

maximum when the QT was decreased from 315 1C to 250 1C, in
coincidence with the maximum fraction of retained austenite and
the lowest fraction of UM. The YS strengthening achieved by
decreasing the QT can be related to the higher stability of the
austenite and a progressive reduction of the UM content. Fig. 11b
relates the values of YS and YS/UTS of Q&P specimens with the
estimated UM contents shown in Fig. 9. Similar values of YS and
YS/UTS were obtained with UM of 0.35 and 0.15 (QT¼ 315 1C and
291 1C, respectively), whereas a progressive increase was observed
reducing the UM fraction from 0.15 to zero (with QT¼243 1C and
253 1C). In general, a contribution by the precipitation of fine
carbides is also possible. The YS of the specimen partitioned at
420 1C (solid symbols of Fig. 11a) was slightly higher than that of
Q&P specimens partitioned at higher temperatures (open symbols)
after quench to similar QT. This can be a consequence of the lower
partitioning temperature and of a partial transformation of the
residual austenite into bainite during partitioning at 420 1C that led
to a higher stabilization of the austenite, reducing the fraction of
untempered martensite in the structure.
The tensile properties obtained after Q&P have the typical low
YS/UTS ratio of these materials (0.6–0.7), with continuous yield-
ing and with the plastic curve characterized by high work
hardening. The continuous yielding indicates a free mobility of
the dislocations but also the presence of the retained austenite,
that reduces the yield stress and transforms into martensite
during the plastic deformation. The conditions with the lowest
QT (240–250 1C) were characterized by YS/UTS¼ 0.80, with con-
tinuous yielding but lower work hardening.
The tensile properties of Q&T steels are summarized in Table 5
and compared with QP243 and QP253 specimens. The specimen
QT500 exhibited UTS and TE quite similar to the Q&P specimens,
while the QT550 had similar elongation but lower UTS. The yield-to-
tensile ratio was a little higher (0.85) and the yield was continuous,
indicating also in this case a high density of mobile dislocations.
4.3.2. Toughness
The CVN tests were carried out to determine the 50% FATT and the
results are reported in Fig. 12a and b. The QP-B and Q&P specimens
with a QT of 240–290 1C displayed a similar behavior in terms of
transition curves and impact energies, although a slight dependence
on the quenching temperature can be observed. At –30 1C all the
materials exhibited a completely brittle fracture, but at higher
temperatures the specimens quenched to QT between 243 1C and
264 1C showed a slightly better performance. At 0 1C and –20 1C the
lowest impact energy was determined for the specimen quenched to
281 1C. This material also reached a lower level of carbon enrichment
494 E. Paravicini Bagliani et al. / Materials Science & Engineering A 559 (2013) 486–495
Fig. 12. Normalized CVN impact energies after heat treatments: (a) as a function
of testing temperature and (b) impact energy at þ 20 1C and FATT as a function of
quench temperature. Material codes are listed in Table 4.
of the austenite in comparison with the sheets QP276 and QP291,
quenched to similar QT (1.25% versus 1.65%). The microstructures
were comparable and an explanation of this difference was not found,
but it is an indication of the variability of the results when the quench
is stopped above the optimum temperature. The sheet QP-B exhibited
an intermediate behavior between these materials.
The 50% FATT of this group of specimens were between
þ10 1C and þ25 1C and only the material with QT¼315 1C, due
to the high fraction of untempered martensite, had a significantly
worse toughness, with a FATT of 60 1C. The Q&T specimens also
exhibited very high transition temperatures.
The best combination of YS and FATT with the selected steel was
therefore obtained by Q&P, quenched at a QT of 240–250 1C,
i.e. reaching YS close to 1200 MPa with FATT 10 1C. This better
behavior may arise from the combined effects of the carbon
depletion of martensite, the absence of the coarse films of carbides
and, on the other hand, the presence of films and islands of
austenite that contribute to the refinement of the microstructure.
The difference between Q&T and Q&P, for this steel, is a reduction of
FATT of 50 1C at similar YS (Table 5) and this shows the potential of
Q&P in improving the YS–toughness combinations.
4.3.3. Comments on industrial feasibility
The results obtained by Q&P are comparable with those
achievable with carbide-free bainitic steels and low-silicon Q&T
steels, although in both cases a careful design of chemical
composition and manufacturing process led to significant
improvements of these properties. This is shown in Fig. 13 that
compares the CVN impact energies obtained in the present study
by Q&P with some data available from the literature of bainitic
and low silicon Q&T steels at comparable YS levels.
90
Ref.5
80
70 Present
study
Impact energy (J)
60 Ref.7
50
Ref.6
40 QP243, QP253, YS = 1170 MPa
Ref. 5 Q&T, YS = 1165 MPa
30 Ref. 7 Bainitic steel YS = 965 MPa
Ref. 7 Bainitic steel YS = 1230 MPa
Ref. 6 Bainitic steel YS = 1150 MPa
20
-120 -100 -80 -60 -40 -20 0 20 40 60 80 100
T C
Fig. 13. Charpy V notch impact energies after Q&P compared with data from the
literature of bainitic steels and Q&T steels.
In the case of Q&P treatments, the microstructural analysis
indicated some difficulties in the achievement of a homogeneous
and complete stabilization of the retained austenite, due to the
precipitation of carbides by autotempering of the martensite
formed in the first quench and the presence of hard phases in
the structure (MA-constituents). The low cooling rates in the final
stage of the first quench and the time needed to reach the PT were
limited by the quenching medium and by the thickness of the
material and prevented the possibility to get a more accurate
control of the Q&P treatment.
An alternative route that could be industrially applied to sheets/
plates as well as to tubular products is a sequence consisting
of (a) induction heating, (b) interrupted accelerated cooling, and
(c) reheating to the partitioning temperature and holding by
induction again. This sequence should meet the need of short
times required by this treatment.
In the perspective of further improvements of DBTT and YS, the
presence of islands of MA should be minimized as much as possible.
On one hand a proper application of Q&P treatments without
the presence of bainite requires that the chemical composition is
modified reducing the Bs-temperature and increasing the incuba-
tion time for the formation of bainite, a result that can be obtained
increasing the content of the alloying elements already present in
the steel. On the other hand, the cooling rate below Ms remains a
critical point, because of the autotempering of martensite. The
presence of local segregation can make critical the use of elements
like manganese that locally decrease the transformation tempera-
tures and delay the progress of the martensitic transformation,
leaving untransformed islands of austenite that have a smaller
chance to be fully stabilized to room temperature.
5. Conclusions
A medium-carbon high-silicon steel was studied to investigate
the effect of different microstructures on the combinations of
strength and toughness comparing the mechanical properties
obtained by Q&P and Q&T:
(a) Dilatometry was used to identify the best conditions to carry
out the Q&P treatments. An optimum quench temperature of
285 1C and a working window for the partitioning step
between 470 1C and 500 1C were identified.
(b) With the Q&P treatments in salt bath, the selected steel reached
the maximum stabilization of the austenite with QT¼250 1C,
achieving, in these conditions, the best combination of YS and
toughness. This result can be attributed to a combination of
 E. Paravicini Bagliani et al. / Materials Science & Engineering A 559 (2013) 486–495
effects: the higher stabilization of the austenite, the carbon
depletion of martensite and the reduction of untempered
martensite fraction. The films and islands of retained austenite
between the blocks and packets of the tempered martensite can
also have a role in the refinement of the Q&P microstructure.
(c) The study of toughness properties with different heat treat-
ments conditions highlighted the importance to avoid islands
of untempered martensite, if the purpose is to combine
high YS and low FATT. The autotempering of martensite was
regarded as the main competing process to the stabilization of
the austenite, leading to the presence of small islands of
austenite that are not sufficiently enriched in carbon to be
stabilised to room temperature.
(d) The Q&T treatment was not appropriate for the selected steel.
The absence of carbon partitioning led to a very poor tough-
ness at similar YS levels, due to the presence of coarse
carbides in the microstructure.
Acknowledgments
Dr. Mario Rossi, director of Tenaris Dalmine Research &
Development Center, is kindly acknowledged for permission to
publish this work.
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