Development of high strength hot rolled low carbon

copper-bearing steel containing nanometer sized

carbides
M.P. Phaniraja, 1, Young-Min Shina, b, 1, Joonho Leeb, Nam Hoon
Gooc, Dong-Ik Kima, Jin-Yoo Suha, Woo-Sang Junga, jae-Hyeok
Shima, In-Suk Choia,

Abstract
A low carbon ferritic steel was alloyed with Ti, Mo and Cu with the
intention of achieving greater increment in strength by multiple
precipitate strengthening. The steel is hot rolled and subjected to
interrupted cooling to enable precipitation of TiMo carbides and
copper. Thermodynamic calculations were carried out to determine
equilibrium phase fractions at different temperatures. Microstructure
characterization using transmission electron microscopy and
composition analysis revealed that the steel contains ~5 nm size
precipitates of (Ti,Mo)C. Precipitation kinetics calculations using
MatCalc software showed that mainly body centered cubic copper
precipitates of size < 5nm form under the cooling conditions in the
present study. The steel has the high tensile strength of 853 MPa
and good ductility. The yield strength increases by 420 MPa, which is
more than that achieved in hot rolled low carbon ferritic steels with
only copper precipitates or only carbide precipitates. The
precipitation and strengthening contribution of copper and (Ti,Mo)C
precipitates and their effect on the work hardening behavior is
discussed.
Keywords
HSLA steel;
Copper;
Nano-sized carbides;
Interrupted cooling;
Numerical simulation
1. Introduction
The long-standing goal in research on high strength steels has been
to increase the strength while maintaining the ductility, toughness,
weldability and cost effectiveness. In low carbon ferritic steels the
strengthductility combination is achieved by microalloying with
elements such as Nb, V or Ti in the mill processed condition without
the requirement of an additional heat treatment. The microalloying
elements form nanocrystalline carbides/carbonitrides which
strengthen the ferrite matrix by grain size refinement and
precipitation strengthening. The conventional microalloyed steels
typically
possess
yield
strengths
in
the
range
450
550 MPa [1] and [2], however significant improvements in strength

can be achieved by a combination of alloy design and thermo

mechanical processing followed by controlled cooling.
Recently, Funakawa et al. [3] reported an increase in yield strength
of 300 MPa in the hot rolled low carbon steel micro-alloyed with Ti
and Mo in equiatomic concentration. The hot rolled sheet was air
cooled to 620 C where phase transformation () was
accompanied by precipitation of alloy carbides. The high strength of
the steel was due to ferrite grain size refinement (~3 m) and
precipitation of nanometer size (Ti,Mo)C carbides (~3 nm). Chen et
al. [4] compared carbide size and hardness of three continuously
cooled ferritic steels containing the microalloying elements Ti, TiMo
and TiNb respectively. They reported that the TiMo steel had the
finest carbide size and highest hardness. The relatively lower
change in carbide size and hardness measurements after different
cooling rates lead them to conclude that the carbide formed in the
TiMo steel was relatively thermally stable.
Copper addition in amounts of 12 wt% has also been used for
precipitation
strengthening
in
low
carbon
structural
steels [5], [6], [7], [8] and [9].
Commercially
available
copper
containing low carbon steels such as ASTM A710 or HSLA80, also
contain microalloying elements such as Nb and have yield strength
between 450 and 520 MPa [10] and [11] in the as-rolled and aircooled condition. The higher strength of these steels is because of
the formation of nanosized copper precipitates in ferrite and grain
refinement brought out by microalloy carbides in prior austenite.
Misra et al. [12] studied the effect of copper addition on the
mechanical properties of hot rolled VNb microalloyed steels. They
reported that increasing the copper content from 0.22 to 0.63 wt%
increased the yield strength by ~25 MPa in the as rolled condition.
In order to increase the strength further they microalloyed the Cu
NbV steel with Ti and Mo. The yield and tensile strength improved
to 554 MPa and 658 MPa, respectively after aging the as-rolled
specimen. The improvement in strength was due to ferrite grain
refinement (210 m), and nano sized precipitates of copper and
the carbides: NbC, VC, Mo2C, Ti(Nb)C. The % elongation decreased
with increase in strength. Their results show that multiple carbide
precipitates may not guarantee the yield strength superior to that
obtained
in
steels
with
fewer
type
of
carbide
precipitates [3] and [13].
In the present study the low carbon steel is alloyed with both
copper, and titanium and molybdenum with the intention of
synergizing their beneficial effect on mechanical properties. The
structure and properties of TiMo and CuTiMo microalloyed steels
were investigated to determine the contributions to strength by Ti
Mo carbides individually and together with copper precipitates. The
thermo-kinetic software MatCalc has been used to calculate
evolution of copper precipitates in Fe1.4% Cu alloy [14] and in
austenitic heat resistant steels by this paper s co-authors [15]. In

the present study MatCalc was used to calculate the phase evolution
and size distribution of copper precipitates.
2. Experimental and computational details
The compositions of steels designated as CMn, TiMo and CuTiMo are
given in Table 1. CMn is the base low carbon steel without any
precipitate forming elements. TiMo and CuTiMo are the CMn steel
microalloyed with titanium and molybdenum, and microalloyed with
copper, titanium and molybdenum respectively. The alloys were
prepared using vacuum induction melting into 5.7 kg ingots. The
ingots were forged and rolled at 1100 C into 15 mm thick slabs.
The slabs were then heated to 1250 C and held for 30 min to
dissolve any precipitates and then rolled to 75% reduction at
900 C. After rolling the specimens were first air cooled to 650 C
and held for 5 min, followed by air cooling to 500 C where it was
held for 60 min and then furnace cooled to room temperature. The
precipitates viz. (Ti,Mo)C carbide and Cu rich phase are expected to
form
at
650 C [3], [4] and [16] and
500 C [17] and [18] respectively.
Table 1.
Chemical composition (wt%).
Steel
C
Mn
Si
Mo
Ti
Cu
Al
Fe
CMn
0.07 1.47 0.32

0.04 Bal.
TiMo
0.07 1.34 0.32 0.20 0.09
0.04 Bal.
CuTiMo
0.07 1.53 0.34 0.21 0.09 1.17 0.04 Bal.
Table options
The specimens for the tension test were prepared from the rolled
plates along the rolling direction according to ASTM standard E08-M
with gage length of 25 mm, gage width of 6 mm and thickness of
2 mm. The tests were carried out at the constant crosshead speed
of 1 mm/min. The tension test experiments were conducted on two
specimens for each composition. The microstructure was
characterized using scanning electron microscope (SEM), the 200 kV
Tecnai 20 transmission electron microscope (TEM) and energy
dispersive spectroscopy (EDS). Focused Ion Beam (FIB) technique
was used to make thin foil specimens for characterization of
precipitates in TEM-EDS. The precipitates were also extracted by
dissolution in the electrolyte solution consisting of 4%
tetramethylammonium chloride, 10% acetone and 86% methyl
alcohol. The grain size was determined from SEM micrographs with
help of an image analyzer using the linear intercept method. The
precipitate
size
and
distribution
were
determined
from
measurements in TEM micrographs on up to 400 extracted particles.
The equilibrium phase fractions at different temperatures were
calculated using Thermo-Calc [19] and [20]. The data set of
parameters for the thermodynamic models describing the FeCMn
SiMoTiCu system used in Themo-Calc was from the TCFE
database incorporated in the software. The phases included in the
calculations were austenite, ferrite, cementite, fcc-copper, and MC

(M=Ti,Mo) carbide. A thermo-kinetic software MatCalc (version

5.30) [21], [22] and [23] was used to determine the precipitation
kinetics and size distribution of Cu precipitates and MC carbides. In
MatCalc the microstructure evolution is calculated based on the
classical nucleation theory. The evolution equations for the radius
and composition of each precipitate are derived from the
thermodynamic extremum principle. The thermodynamic and kinetic
data required for the simulation are calculated from the MatCalc
database mc_steel, version 1.18, and the MatCalc mobility
database mc_sample_fe, version 1.007. The following assumptions
were made for the simulation: (i) average grain size and dislocation
density of austenite is 50 m and 1012 m2, (ii) average grain size
and dislocation density of ferrite is 15 m and 1013 m2, (iii)
nucleation of bcc Cu and MC precipitates occurs on grain boundaries
and dislocations, (iv) the austeniteferrite transformation occurs at
650 C and (v) the bcc Cu precipitates transform into fcc Cu
precipitates when they grow in a range between 35 nm.
3. Results
3.1. Phase equilibria
The equilibrium phase fractions calculated using ThermoCalc are
plotted as a function of temperature in Fig. 1. In all the steels
cementite precipitates below ~700 C and precipitation of face
centered cubic (fcc) copper begins at around 750 C. In steels
containing Ti and Mo MC carbide (NaCl structure) precipitates,
consisting mainly of TiC, start to form around 1150 C. In these
steels the volume fraction of cementite is relatively lower than that
in CMn steel. The lower cementite content is expected because
some carbon is used up in the formation of MC type precipitates.
Fig. 1.
Calculated equilibrium phase fractions plotted as a function of
temperature in (a) CMn steel, (b) TiMo steel and (c) CuTiMo
steel.
Figure options
3.2. Microstructure
The microstructure in all the steels consists mainly of polygonal
ferrite (Fig. 2). In the CMn steel cementite exists in pearlite form
whereas in TiMo and CuTiMo steels pearlite colonies are less
common. The latter is consistent with the calculations of equilibrium
phase fractions (Fig. 1) where it was noted that the lower fraction of
cementite was because some carbon was used in the formation of
MC carbides. The ferrite grain size of CMn steel is 16 m whereas
both TiMo and CuTiMo steels have relatively finer grain size of
12 m.

Fig. 2.
SEM micrographs of the steels after hot rolling and cooling: (a)
CMn steel, (b) TiMo steel and (C) CuTiMo steel.
Figure options
Fig. 3a is a TEM micrograph of the extracted nanometer size carbide
particles from TiMo steel. The electron diffraction pattern from the
precipitates shows that they have a typical face centered cubic
structure (Fig. 3b). The lattice parameter calculated based on the
diffraction ring diameter is 0.430 nm which is similar to that of TiC
(0.433 nm). The EDS spectrum shows that MC precipitates contains
Ti and Mo as main components (Fig. 3c). The copper peak (at ~8 eV)
in the EDS spectrum is from the Cu grid that supports the carbon
extraction replica. The composition analyses showed that MC
precipitates contain molybdenum and titanium in the atomic
concentration ratio between 0.2 and 0.4. This indicates that the
precipitates are indeed (Ti,Mo)C precipitates. The precipitates have
size in the range from 2 nm to 7 nm (Fig. 3d).

Fig. 3.
(a) TEM micrograph showing precipitates extracted from TiMo
steel, the corresponding, (b) fcc diffraction pattern, (c) EDS
Spectrum from the precipitates, and (d) distribution of carbide
size.
Figure options

Fig. 4 shows the diffraction pattern and bright field and dark field
images from the foil specimen of the CuTiMo steel. The diffraction
rings for (110)-Fe and for (111) and (200) from TiC are overlaid on
the diffraction pattern. The diffraction pattern has been inverted i.e.
the diffraction spots are now black and the background is white-grey
to enable clearer identification of spots from carbide. The dark field
image for the spot marked A in the diffraction pattern shows the size
of the carbide particles. The particle size of the carbides in the
present study was measured, like in the TiMo steel, from
transmission electron micrographs of extracted precipitates and
found to be in the range from 2 nm to 8 nm (Fig. 4d). Composition
analysis showed that the Mo/Ti atomic concentration ratio, like in
the TiMo steel, was in the range 0.20.4.

Fig. 4.
(a) Bright field and (b) dark field image corresponding to the
spot marked A in the diffraction pattern (c) from the CuTiMo
steel and (d) size distribution of extracted precipitates.
Figure options

In the CuTiMo steels the copper precipitates could not be identified

in the electron microscope. However, simulations using MatCalc for
the processing temperaturetime conditions employed in the
present study showed that bcc-copper precipitation initiated in the
ferrite matrix and reached saturation (Fig. 5a) and fcc-copper
precipitates have begun to form. The precipitates are mainly body
centered cubic and their size is largely between 2.4 nm and 3 nm
(Fig. 5b). A small fraction of precipitates having size larger than
3 nm have transformed to the face centered cubic structure. The
~3 nm precipitates are fully coherent with the matrix and cannot be
observed
in
the
TEM
because
of
poor
diffraction
contrast [24] and [25]. However, in a parallel unpublished work, by
the present authors, on a 1.7 wt% Cu steel under similar processing
conditions fcc-copper precipitates of size 613 nm formed and could
be easily identified.

Fig. 5.
Kinetics of copper precipitation in CuTiMo (a) and precipitate
size distribution (b).
Figure options
3.3. Mechanical properties
The strength of the CMn steel increases with microalloying additions
significantly (Fig. 6a). The yield stress,y, of the TiMo steel (642 MPa)
is more than 2.4 times that of CMn steel ( Table 2). The CuTiMo steel
has the highest yield (732 MPa) and tensile strength (853 MPa). The
% elongation of both TiMo and CuTiMo steels is similar (16%) but
lower than that of the CMn steel (33%).

Fig. 6.
Engineering stress-elongation (a) and work hardening ratereduced stress (y) curves (b) for CMn, TiMo and CuTiMo
steels.
Figure options
Table 2.
Measured yield strength (YS), tensile strength(TS), %
elongation and calculated precipitation strengthening
contribution and increment in YS due to finer grain size (g).
YS
TS
%
Steel
(MPa)
(MPa)
Elongation
ppt a (MPa) g (MPa)
CMn
267
401
33

TiMo
642
770
16
354
21
CuTiMo 732
853
16.6
417
21
a
ppt is the increment in yield strength due to precipitates.
Table options
In order to compare the effect of alloying additions on the work
hardening rates, the engineering stressstrain curves were first
transformed into true stresstrue strain curves. The data between
the yield stress and the maximum stress were then fitted to a
polynomial and this polynomial was then differentiated with respect
to strain. Fig. 6b shows the work hardening rate, d/d plotted as a
function of the reduced flow stress, y, for the three steels.
Typically there is a high initial work hardening rate followed by a
decrease as deformation proceeds. The initial work hardening rate
increases from ~3100 MPa in the CMn steel to ~4100 MPa in the
TiMo steel. The CuTiMo steel has an initial work hardening rate
marginally higher than the TiMo steel, however, the slope of the
work hardening rate curve is initially lower and in the later stages of
deformation is similar to the TiMo steel.
4. Discussion
4.1. Microstructure

The solubility of titanium in ferrite is low thereby cooling the steels

after hot rolling to 650 C supersaturates ferrite and results in the
precipitation of alloy carbides during subsequent cooling. The alloy
carbide precipitates contained molybdenum and titanium in the
Mo/Ti atomic concentration ratio of 0.20.4 indicating that they
could have formed over range of temperatures. A thermodynamic
equilibrium calculation was carried out to determine the Mo/Ti
atomic ratio as a function of temperature. The Mo/Ti atomic
concentration ratio decreased with increasing temperature and
reached 0.2 at ~600 C (Fig. 7). Therefore the precipitates observed
in the present study have most likely formed below 600 C. Chen et
al. [4] have reported similar precipitation from supersaturated ferrite
when they cooled (Ti,Mo)C forming steels at different cooling rates.
Fig. 7.
The atomic concentration ratio Mo/Ti in MC carbide
precipitates in TiMo steel, obtained from thermodynamic
equilibrium calculations, plotted as a function of temperature.
Figure options
The Fe-base copper alloys [5], [24] and [26] on aging, usually in the
temperature range 400650 C, initially form metastable bcc copper
precipitates. As these precipitates grow they transform to the 9R
structure [27]and then at relatively larger size to the stable fcc
structure. The metastable bcc structure is maintained up to a size of
2.43 nm [18] and [28]. The peak hardness during aging is achieved
when the precipitates have the bcc structure. The size of copper
precipitates in the CuTiMo steel is largely between 2.4 and 3 nm.
Thereby, the strengthening due to copper precipitates in the CuTiMo
steel should be analogous to that of the steel in the peak aged
condition. Indeed the significant improvement in yield strength after
adding copper to the TiMo steel, calculated in the next section, is
mainly due to the bcc copper precipitates.
4.2. Estimating precipitation strengthening contributions
The base composition of the steels is similar to CMn steel and the
microstructure consists mainly of ferrite with some pearlite. Thereby
the contribution to yield strength after alloying can be estimated by
deducting the yield strength of CMn steel. The contribution to yield
strength from precipitates can be determined after accounting for
solid solution strengthening and grain size strengthening using
Eq. (1).
equation(1)
Turn MathJaxon

where g is the increment in the contribution because of the

slightly finer grain size of TiMo and CuTiMo steels, when compared
with CMn steel, calculated using 17.402 d1/2 [3] and [29] and Cu is
the contribution from solid solution strengthening by copper (38 MPa
per wt% Cu [1]). The amount of copper remaining in solution after
precipitation was calculated to be 0.7 wt%; this amount was used to
calculateCu in Eq. (1). The solubility of titanium and molybdenum in
ferrite is low and is assumed to have negligible solid solution
strengthening effect. The precipitation strengthening contributions
calculated using Eq. (1) are given in Table 2. The increment in yield
strength due to precipitation in TiMo steel is 347 MPa. This is
comparable to the 340 MPa improvement in yield strength reported
on low carbon steels alloyed with Ti and Mo and processed under
different conditions [3]. The precipitation strengthening contribution
in the CuTiMo steel is 420 MPa which is more than one and half
times the yield strength of the CMn steel.
4.3. Work hardening
In a matrix with non-shearable precipitates the moving dislocations
bypass the particle forming a loop around the particle rather than
cut it. Thereby, the effective spacing between particles is effectively
reduced and the stress required to move another dislocation past
the

particle

increases

according

to

the

AshbyOrowan

mechanism [30]. The dislocation loop exerts a back stress which

must be overcome for additional slip to take place. Consequently
the matrix strain hardens rapidly as more dislocation loops form
around the particle. The (Ti,Mo)C precipitates, formed in the present
study, are hard and the dislocations should by pass the particles,
form loops around them, and thereby give rise to the significantly
higher work hardening rate (Fig. 6). Indeed dislocation loops have
been observed in deformed (Ti,Mo)C forming steels [31].
Copper precipitates are elastically soft and can be sheared by the
moving dislocations [26]. Nakashima et al.[32] have reported that in
FeCu alloys moving dislocations cut and pass through copper
particles of size up to 70 nm. Once the particles are sheared the
resistance to further dislocation motion decreases which should
result

in

the

lowering

of

the

macroscopic

strain

hardening

rate [33] and [34]. The increase in strength on copper addition and
marginal increase in the initial work hardening rate (Fig. 6), when
compared with the TiMo steel, are in accordance with the hypothesis

noted above. However, the macroscopic work hardening rate

becomes similar to the TiMo steel in the later stages of deformation.
This could be explained as follows. The copper precipitates in the
present study have a size close to the size at which transformation
to

the

9R

structure [27] occurs.

It

is

possible

that

during

deformation bcc copper particles with size around 3 nm transformed

to the stronger 9R structure which increased the hardening rate
such that the slope of the work hardening rate curve becomes
similar to the TiMo steel in the later stages of deformation (Fig. 6b).
Similar arguments have been posed by Militzer et al. [35] in their
study where FeCu alloys exhibited higher work hardening rate
when the size of copper precipitates was close to the size at which
transformation occurs. However, further study is needed to validate
the hypothesis of the dynamic transformation and the associated
change in the hardening rate.
4.4. Ductility
Ductile failure is initiated by nucleation of voids at hard second
phase particles such as carbides and nitrides in steels. At large
strains the dislocation structure around the particle imposes high
local stress that upon reaching a critical value will cause decohesion
of the particle/matrix interface thereby nucleating a void. Particles
as small as 5 nm have been found to nucleate voids [36]. The
relatively lower ductility of the TiMo steel when compared with the
CMn steel is thereby likely due to void nucleation at the
carbide/matrix interface. Typically, increasing the volume fraction of
hard second phase decreases the ductility[37] and [38]. However,
there is no decrease in the ductility of the CuTiMo steel where the
matrix has copper precipitates in addition to carbide particles. This
is because, as noted above, the moving dislocations cut and pass
through the relatively soft copper particles resulting in only a
marginal increase in work hardening rate. Consequently the
increase in the local stress is lower than that required for particle
matrix decohesion and the ductility remains unaffected.
5. Summary and conclusions

Three low carbon steels: a plain low carbon steel, microalloyed with
Ti and Mo, and microalloyed with Cu, Ti and Mo were prepared and
subjected to hot rolling followed by interrupted cooling. ThermoCalc
was used to determine equilibrium phase fractions at different
temperatures. MatCalc was used to simulate the precipitation
kinetics and determine size distribution of copper precipitate. The
microstructure was characterized using SEM, TEM and EDS. The
specimens

were

tested

in

tension

to

determine

mechanical

properties.
1.
Alloying with Cu, Ti and Mo increases the yield strength of the
low carbon ferritic steel from 267 MPa to 732 MPa and tensile
strength from 401 MPa to 853 MPa.
2.
Fcc (Ti,Mo)C carbides of ~5 nm diameter and bcc Cu-rich
precipitates of <5 nm diameter form in the ferrite matrix.
3.
The increment in yield strength due to the precipitation
strengthening effect of carbides in the TiMo steel is 347 MPa.
The alloy carbides are hard and moving dislocations by-pass,
form loops around them giving rise to the significantly higher
work hardening rate.
4.
The precipitation strengthening contribution of copper and
carbide precipitates jointly, in the CuTiMo steel, is 420 MPa.
This is more than the increments in yield strength that would
be achieved with only copper precipitates or only carbide
precipitates. Though the total fraction of precipitates in the
CuTiMo steel has increased the ductility is not adversely
affected because of the shearable copper precipitates.