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Effect of Cu, Cr and Ni on mechanical properties of 0.15 wt.% C TRIP-

aided cold rolled steels

Article in Scripta Materialia · March 2003

DOI: 10.1016/S1359-6462(02)00477-3

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 Scripta Materialia 48 (2003) 539–544
www.actamat-journals.com

Effect of Cu, Cr and Ni on mechanical properties

of 0.15 wt.% C TRIP-aided cold rolled steels
Sung-Joon Kim *, Chang Gil Lee, Tae-Ho Lee, Chang-Seok Oh
Department of Materials Processing, Korea Institute of Machinery and Materials, 66 Sangnam-dong, Changwon City,
Kyungnam 641-010, South Korea
Received 6 August 2002; received in revised form 25 September 2002; accepted 2 October 2002

Abstract
Cold-rolled steels based on 0.15C–1.5Mn–1.5Si–0.5Cu containing Cr or/and Ni were prepared, and intercritical
annealing and isothermal treatment, were carried out. The addition of Cu or Cu þ Ni resulted in a large increase of the
retained austenite volume fraction as well as an improvement of elongation and the strength-ductility balance. How-
ever, the addition of Cr or Cu þ Ni showed a dual-phase deformation behavior having higher tensile strength and lower
elongation.
Ó 2002 Acta Materialia Inc. Published by Elsevier Science Ltd. All rights reserved.

Keywords: Multiphase steels; TRIP effect; Tramp elements; Mechanical properties

1. Introduction aided multiphase steels based on Fe–C–Mn–Si,

With ever increasing environmental require-
ments, the challenges ahead steelmakers are im-
mense. As one example, the usage of scrap in
steelmaking process increased and the accumula-
tion of tramp or trace elements becomes a big
problem due to their harmful effect on the me-
chanical properties and formability [1]. The chal-
lenges facing the industry are therefore to reduce
the cost for refining the tramp elements and
maximize the recyclabililty of steel scraps.
Recently, numerous studies have been carried out
on the transformation induced plasticity (TRIP)
*
Corresponding author. Tel.: +82-55-280-3334; fax: +82-55-
280-3498.
E-mail address: sjkim@kmail.kimm.re.kr (S.-J. Kim).
since the TRIP steels are good candidates for en-
vironmentally conscious materials owing to their
simple composition and excellent combinations of
high strength–high ductility [2–6]. In addition,
various mechanical properties can be attained by
thermomechanical processing. Typical TRIP steels
consisting of 0.2–0.4% C, 1.0–2.5% Mn, and 1.2–
2.0% Si have been widely studied for the last two
decades in order to achieve better combinations of
strength and ductility [5–8] and to understand the
basic physical metallurgy. However, in order to
utilize more steel scrap and widen the application
of TRIP steels, it is necessary to investigate the
exact effect of tramp elements on the TRIP be-
havior and material characteristics. In the present
study, therefore, tramp elements such as Cu, Ni,
and/or Cr were added to Fe–0.15%C–1.5%Mn–
1.5%Si TRIP-aided cold rolled steels, and their

1359-6462/03/$ - see front matter Ó 2002 Acta Materialia Inc. Published by Elsevier Science Ltd. All rights reserved.
PII: S 1 3 5 9 - 6 4 6 2 ( 0 2 ) 0 0 4 7 7 - 3
540 S.-J. Kim et al. / Scripta Materialia 48 (2003) 539–544

Table 1
Chemical compositions (wt.%) and transformation temperatures (°C) estimated from empirical formula derived by Andrews [9]
Steel C Mn Si Cu Cr Ni AC1 AC3 MS
ECO-6 0.14 1.51 1.49 0.51 – – 750 900 432
ECO-7 0.15 1.51 1.52 0.51 0.39 – 757 899 425
ECO-8 0.15 1.52 1.53 0.51 – 0.41 744 892 423
ECO-9 0.15 1.50 1.55 0.50 0.39 0.41 751 892 418

effects on the volume fraction of retained auste-
nite, mechanical properties and microstructures
were elucidated.
2. Experimental procedure
Four ingots based on Fe–0.15C–1.5Mn–1.5Si
were vacuum induction melted, and their chemical
compositions are given in Table 1, together with
AC1 , AC3 and MS transformation temperatures es-
timated from empirical formulae derived by An-
drews [9]. Each ingot of 25 kg was hot rolled to
3.0 mm thickness with finishing temperature
around 900 °C. Hot rolled strips cooled in air were
chemically polished with 80% HCl solution and
cold rolled to 1.0 mm thickness. Tensile specimens
of 25.4 mm long and 6.3 mm wide were machined
with their tensile axis oriented transverse to the
rolling direction.
Tensile specimens were heat treated according to
the schedules shown schematically in Fig. 1. Since
it was found in a former study [10] that the best
combination of strength and ductility was ob-
tained when the volume fractions of ferrite (a) and
austenite (c) were 50% each, the intercritical an-
nealing was carried out at 780 or 790 °C for 5 min
in a salt bath in order to obtain the same fractions
of a and c. The annealed specimens were isother-
mally heat treated at 430 °C for 1–20 min in a low
temperature salt bath followed by water quench-
ing.
Tensile tests were conducted at a crosshead
speed of 2 mm/min using a servo-hydraulic me-
chanical testing machine at ambient temperature.
Microstructures were investigated by optical mi-
croscopy and scanning electron microscopy (SEM).
The retained austenite content of samples before
and after tensile testing was determined by X-ray
diffraction using monochromatic Mo–Ka radia-
tion [11].
3. Results
3.1. Microstructures

Fig. 2 shows the optical micrographs of sam-

ples isothermally heated at 430 °C for 5 min and
etched with sodium metabisulphite solution, in
which gray areas are ferrite, and the white islands
or spots indicate retained austenite. Black areas
are bainite or martensite. All samples contain re-
tained austenite with various shapes. Almost all of
the retained austenite coexists with ferrite, bai-
nite or martensite, and a small amount of retained
austenite having a spherical shape is isolated inside
the ferrite grains. In addition, film-like austenite
is hardly observed along ferrite or lath-like bai-
nite boundaries. The amount of retained austenite
Fig. 1. Schematic drawing of the heat treatment process in this varies depending on alloying content. While the
study. base alloy, ECO-6 (Fig. 2a) and Ni-containing
 S.-J. Kim et al. / Scripta Materialia 48 (2003) 539–544 541

Fig. 2. Optical micrographs of the (a) ECO-6, (b) ECO-7, (c) ECO-8 and (d) ECO-9 isothermally heated at 430 °C for 5 min and etched
with sodium metabisulphite solution.

alloy, ECO-8 (Fig. 2c), have 16% and 18% of re-

tained austenite, respectively, Cr-containing al-
loys, ECO-7 (Fig. 2b) and ECO-9 (Fig. 2d), have
only 10% of retained austenite.

3.2. Mechanical properties and retained austenite

Tensile stress–strain curves of all samples iso-

thermally heated at 430 °C for 5 min are given
in Fig. 3. Two types of stress–strain curves were
obtained; continuous and discontinuous yielding
behavior. The ECO-7 and ECO-9 alloys contain-
ing Cr and Cr þ Ni, respectively, show a continu-
ous yielding behavior similar to that of high
strength ferrite–martensite dual phase steel. Ten-
sile strengths ranging from 960 to 1080 MPa with
Fig. 3. Tensile stress–strain curves of the samples isothermally
elongations around 20% were obtained in those heated at 430 °C for 5 min.
samples. Continuous yielding behavior is consid-
ered to be due to the smaller volume fractions of
retained austenite and a large amount of marten- ECO-9 steels. On the other hand, a discontinuous
site formed during cooling. Thus, the dual phase yielding behavior was observed in ECO-6 and
strengthening effect is considered to be more ECO-8 samples. In general, yield point phenomena
dominant than the TRIP effect in ECO-7 and occur in low carbon mild steel, and an upper yield
542 S.-J. Kim et al. / Scripta Materialia 48 (2003) 539–544

point and a lower yield point are observed. How-

ever, in ECO-6 and ECO-8 steels, yield point
elongation occurred almost at the same stress level
and the upper and lower yield points were not ob-
served. Although Sakuma reported that the yield
point elongation in TRIP steel is due to the low
density of dislocations in ferrite grains [12], further
research is needed on the behavior of retained
austenite during the initial stage of plastic defor-
mation in order to elucidate the exact yield point
elongation in TRIP steel.
Fig. 4 shows changes of yield strength (YS),
tensile strength (TS), elongation (EL) and the
strength-ductility balance (TS  EL) as a function
of isothermal holding time. Yield strengths of
ECO-6 and ECO-8 steels increased largely from
the 400 to 500 MPa level due to the formation of
bainite. Tensile strengths were maintained at an
almost constant level of 800 and 850 MPa, re-
spectively, after holding for 3 min. The elongations
of ECO-6 and ECO-8 steels were larger than 30%
regardless of holding time, and their maximum
values reached 38% and 34%, respectively. Tensile
strengths of ECO-7 and ECO-9 steels were 960–
1020 and 1060–1120 MPa, respectively. Although
tensile strengths of ECO-7 and ECO-9 are much
higher than those of ECO-6 and ECO-8 steels,
tensile elongation of ECO-7 steel was less than
24% and that of ECO-9 steel was less than 18%.
The strength-ductility balances which might be
used for evaluating formability were measured as
over 30000 MPa% in ECO-6 and ECO-8 steels,
and below 23,000 MPa% in ECO-7 and ECO-9
steels. Thus, it is considered that steel sheets con-
taining Cu (ECO-6) or Cu þ Ni (ECO-8) have
desirable formability inevitable for applications of
sheet metals, and Cr containing steels have poor
formability.
The above mentioned mechanical property
change is closely related to the amount of retained
austenite after isothermal heat treatment. Fig. 5
shows the volume fraction change of retained auste-
nite as a function of isothermal holding times. The
maximum volume fractions were obtained after 5 Fig. 4. Mechanical properties of the samples isothermally he-
min holding in ECO-6 and ECO-8 steels, and their ated at 430 °C as a function of holding time.
values were 16% and 18%, respectively. When
compared with Fig. 4, isothermal holding condi- tained austenite are nearly consistent with those
tions for the maximum volume fractions of re- for the maximum strength-ductility balances.
 S.-J. Kim et al. / Scripta Materialia 48 (2003) 539–544
Fig. 5. Retained austenite volume fraction changes of the
samples isothermally heated at 430 °C as a function of holding
time.
However, in ECO-7 ad ECO-9 steels, volume
fractions of retained austenite are less than 10%
and their changes with isothermal holding times
are also small. Thus, the elongations and strength-
ductility balances of ECO-7 and ECO-9 steels are
rather low, and the variations of mechanical
properties with isothermal holding times are small.
4. Discussions
In developing high strength and ductile cold
rolled TRIP steel sheets, it is important to find an
optimum chemical composition and heat treat-
ment condition in order to form large volume
fractions of retained austenite. In the present study,
TRIP-aided multiphase low carbon steels contain-
ing tramp elements (Cu, Ni, Cr) are designed,
having high strength and ductility with a good
recyclability.
The addition of Ni to the base alloy ECO-6
enhances tensile strength and ductility along with
the increase of retained austenite volume fraction,
as shown in Figs. 3–5. Nickel is a typical auste-
nite stabilizer, and contributes to the formation of
543
large amount of retained austenite and enhance-
ment of mechanical properties. In addition, Cu is
an austenite stabilizer like Ni [13] and gives a
beneficial effect on the formation of retained aust-
enite resulting in the increase of strength-ductility
balance. Thus, it was confirmed that Ni and Cu
might be used as beneficial tramp elements in im-
proving the mechanical properties of low carbon
TRIP steels.
The addition of Cr or Cr þ Ni revealed a quite
different behavior from Ni added steel. In this
case, while tensile strength increased remarkably,
retained austenite volume fractions and elon-
gations decreased in large amount, which is a
typical tensile behavior of dual phase steels. Cr is
a ferrite stabilizer. From the phase diagram of Fe–
Cr, it is known that the addition of only 0.4 wt.%
of Cr already stabilize ferrite in the temperature
range of 780–790 °C. Thus, transformation from
austenite to ferrite would proceed very actively
during holding in this temperature range, and
other elements like C, Mn, and Ni could be solu-
tionized into austenite and enhance the formation
of retained austenite. However, contrary to this
suggestion, retained austenite volume fractions of
Cr containing steels (ECO-7 and 9) were lower
than those of Cr-free steels (ECO-6 and 8). The
reasons for the opposite result might be as follows.
Though Cr is a ferrite, it also causes the increase
of austenite hardenability. The addition of Cr in
order to increase hardenability is frequently ap-
plied in microalloying steels. If the cooling rate
after isothermal holding is rapid, almost all the
austenite transforms to martensite. In this case, it
would be difficult to expect the improvement of
ductility owing to TRIP effect because of the de-
crease of retained austenite. For the Cr containing
steels, it would be necessary to slow down the
cooling rate after isothermal heat treatment and
refrain from transforming to martensite.
In the meantime, mechanical properties of ECO-
6 steel are superior to those of Cu-free steel when
they were intercritically annealed and isothermally
transformed at the same condition [14]. Im et al.
reported that tensile strength and elongation of
Cu-containing Fe–0.15C–1.5Mn–1.5Si multiphase
steel were 817 MPa and 36.4%, while those of Cu-
free steel were 727 MPa and 29.2%, showing the
544 S.-J. Kim et al. / Scripta Materialia 48 (2003) 539–544
superior tensile properties of Cu-containing steel.
Generally, Cu is known to precipitate very fine
e-Cu in ferrite grains and contributes to precipi-
tation hardening [15]. In Cu-containing steels,
precipitation of e-Cu has been reported only in the
specimens containing over 1.0 wt.% Cu and after
aging tens of minutes in the temperature range
400–700 °C [16,17]. Since the Cu content of ECO-6
was only 0.5% and the isothermal transformation
was carried out at 430 °C for 20 min, it was diffi-
cult to expect the precipitation of e-Cu. Thus, the
increase of yield and tensile strength in Cu-added
ECO-6 steel compared with Fe–0.15C–1.5Mn–
1.5Si steel is considered to be due to the TRIP
effect from higher fractions of retained austenite
and solid solution hardening effect of Cu in ferrite
grains. In addition, Cu is an austenite stabilizer
like Ni [13] and gives a beneficial effect on the
formation of retained austenite resulting in the
increase of strength-ductility balance. Therefore,
Cu can be utilized as a beneficial tramp element
in enhancing the mechanical properties of TRIP-
aided cold rolled sheet steels.
5. Conclusions
1. With the addition of Cu or Cu þ Ni, volume
fraction of retained austenite increases and re-
sults in an excellent combination of strength
and ductility. Tensile strengths ranging 800–
850 MPa with large elongations of 34–38% were
attained from Cu or Cu þ Ni containing steels.
2. The addition of Cr or Cr þ Ni to the base steel
shows a ferrite–martensite dual phase tensile be-
havior having high strength (over 1000 MPa)
and rather low ductility (around 20%).
3. Copper and Ni are austenite stabilizing ele-
ments giving beneficial effects on the formation
of retained austenite. On the other hand, Cr in-
creases hardenability of austenite and results in
the formation of martensite after isothermal
transformation.
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4. It is confirmed that tramp elements like Cu, Ni
and Cr can be utilized to design an excellent
ECO-material having various mechanical prop-
erties with good recyclability.
Acknowledgements
This work was financially supported by the
Ministry of Science and Technology of Korea,
under the National Research Laboratory pro-
gram.
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