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Influence of Co and Al on Bainitic Transformation in
Super Bainitic Steels
Feng Hu, Kai-Ming Wu, and Hua Zheng

The effect of cobalt and aluminum addition on the bainitic transformation of super bainitic
steels was investigated. Nanostructured bainitic ferrite and retained austenite
microstructures were obtained when the steels were transformed at low temperatures.
The bainitic transformation was accelerated by the addition of Co and Al. The thickness of
bainite plate was reduced and the volume fraction of bainite was increased in the Co and
Al containing steel, compared with the parent steel.

1. Introduction 2. Design of Nanostructured Bainitic Steels

With the great demand on resource-saving and energy-
saving, it is of necessity to develop high performance low
cost steels. High performance steels, especially extremely
high strength and good toughness steels, have wide appli-
cation in the manufacturing of aircraft engine shafts, auto-
motive and truck parts, crane arms, protective armors, and
other important structures.[1–4] The main goal is to reduce
the weight and to improve the safety of the structures.
The quenched and tempered martensitic steels and
nickel and molybdenum-rich maraging steels can satisfy
the demand of high-strength and high-toughness.[5–7]
However, they are sensitive to cracking during quenching,
energy-consuming in the manufacturing and expensive in
alloying of the steel. In order to overcome these drawbacks
of quenched and tempered martensitic steels and marag-
ing steels, carbide free bainitic steels has been developed
since last decades. Many of the bainitic steel types cur-
rently exploited commercially are designed experimen-
tally, mainly referring to a continuous-cooling-
transformation mode.[8] New high-strength and high-
toughness carbide free bainitic steels have been recently
designed using models based on phase transformation
theory alone.[9–11] The design of such alloys could be done
without recourse to trial and error.[12–14] The aim of the
present work is to design theoretically nanostructured bai-
nitic steels and to investigate the advanced microstruc-
tures of nano-sized bainitic ferrite and retained austenite.
Transformation can be accelerated by increasing the free
energy change accompanying the austenite (g) to ferrite (a)
transformation. This has to be done without compromising
the hardenability of the system if other high-temperature
phases are to be avoided. It is well-known that both cobalt
and aluminum increase the free energy change.[15] The
basic alloy composition stated in Table 1 is therefore
modified to create an Alloy 2, which contains cobalt and
aluminum, and Alloy 1 is designed for comparison.
It is worth noting that an increase in the driving force at
constant temperature may be beneficial in further refining
the microstructure in two ways, by promoting the for-
mation of a greater quantity of bainitic ferrite, thereby
eliminating islands of retained austenite, which are known
to be detrimental to mechanical properties.[16] It is the
films of retained austenite between the plates of bainitic
ferrite which are desirable. A second advantage could be a
refinement of the size of the bainitic ferrite plates them-
selves, because an increase in the driving force stimulates a
greater number density of plates.[17]
Calculations of the driving force for the transformation
of austenite into ferrite of the same composition, DGg/a,
were carried out using MUCG83.Mod program,[18] con-
firming the expected effect[15] of cobalt and aluminum
on the relative stabilities of austenite and ferrite
(Figure 1a). The effect of Co and Al addition on the shifting
of TTT curves were also calculated for the heat treatment of
bainitic steels (Figure 1b).

[] F. Hu, Prof. K. M. Wu, H. Zheng

International Research Institute for Steel Technology, Wuhan
University of Science and Technology, Wuhan 430081, China
3. Experimental
Email: wukaiming@wust.edu.cn, wukaiming2000@yahoo.com
Steel ingots of the composition of Alloy 1 and Alloy 2,
DOI: 10.1002/srin.201200334 shown in Table 1, were provided by Corus UK, hot rolled

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Alloy C Si Mn
1 0.79 1.59 1.94
2 0.78 1.60 2.02
Table 1. Chemical composition of designed alloys.
Figure 1. Effect of the addition of Co and Al of bainitic transformation. a) The free energy change DGga as a function of temperature
and b) the shifting of TTT curves.
down to slabs of 40 mm thickness. Samples were cut and
then homogenized at 12008C for 48 h in a vacuum furnace.
Then they were left in the furnace to cool down to room
temperature over a period of 24 h to obtain a fully pearlitic
microstructure. The slow cooling was necessary to avoid
athermal martensite formation which may introduce
cracks, thus permanently affecting the integrity of the
sample. Samples were then machined from the relatively
soft homogenized lumps which are pearlitic, since the
bainitic microstructure is too hard to easily machine.
In order to ensure complete dissolution of cementite
present in the as-homogenized pearlitic structure during
subsequent austenitization, steel samples were austeni-
tized at 10008C for 15 min. To avoid oxidation, austeniti-
zation was carried out in a tube furnace with a continuous
flow of commercial purity argon. Prior to austenitization,
during sample loading at moderate temperatures, the fur-
nace was evacuated and repeatedly flushed with agron.
After holding at the g-phase field for sufficient time to
ensure a fully austenitic state but not so long to give grain
coarsening, the samples were transformed at temperatures
ranging from 200 to 3008C for different times in another
low temperature furnace before quenching into water.
X-ray experiments were conducted using a Phillips
PPW1730 diffractometer and a scanning rate (2u) of
0.1 min1 over the range 2u ¼ 30–1108, with unfiltered Cu
Ka radiation. The system was operated at 45 kV and 45 mA.
It has been utilized to determine the volume fraction of
retained austenite and bainitic ferrite were calculated by
means of integrated intensities of the (111), (200), (220),
and (311) austenite peaks, the (110), (002), (112), and (022)
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Mo Cr Co Al
0.30 1.33 – 0.013
0.24 1.01 3.87 1.37
bainite peaks.[19,20] The measurement error of retained
austenite volume fraction was 0.015. The carbon concen-
tration in austenite and ferrite were estimated by using the
measured lattice parameters.[20,21] The carbon content in
austenite xg and ferrite xa can be estimated by using
equations. The calculation error of carbon concentration
in austenite and ferrite were about 0.10 wt%.
ag ¼ 3:5780 þ 0:033xC þ 0:00095xMn  0:0002xNi þ 0:0006xCr
þ 0:0056xAl þ 0:0031xMo þ 0:0018xV
ðaFe  0:279MC Þ2 ðaFe þ 2:496MC Þ  a3Fe
aa ¼ 2:8664 þ
3a2Fe
 0:03MSi þ 0:06MMn þ 0:07MNi þ 0:31MMo þ 0:05MCr
þ 0:096MV
where ag and aa represent the lattice parameter of austen-
ite and ferrite in Å, respectively. xi is the concentration of
element i in weight percent, Mi is the concentration of
element i in mole fraction and aFe ¼ 2.8664 Å is the
parameter of ferrite in pure iron.
After heat treatment specimens were polished and
etched with 3 vol% nital solution for microscopy analysis.
Microstructural observations were made using scanning
and transmission electron microscopy. Specimens for
transmission electron microscopy were machined from
3 mm diameter rods which were sliced into 100 mm discs.
These were ground down to 50 mm thickness using 1200
grit silicon carbide paper, for electropolishing at 50 V using
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Figure 2. SEM micrographs of bainite isothermally held at 2008C. a) Alloy 1 for 192 h and b) Alloy 2 for 78 h.

Figure 3. TEM images of lamellar bainitic structure. a) Alloy 1 for 192 h and b) Alloy 2 for 78 h.

a twin-jet unit. The electrolyte consisted of 5% perchloric
acid, 15% glycerol, and 80% methanol. A JEOL JEM-200CX
transmission electron microscope operated at 200 kV was
used to examine the thin foils. Transmission electron
microscopy was performed to determine the true plate
thicknesses t, by measuring the mean lineal intercept
LT ¼ pt=2 in a direction normal to the plate length. The
thickness t is related to the mean lineal intercept measured
using randomly oriented test lines by the relation
L ffi 2t,[22,23] but LT is easier to measure since it is rare in
transmission electron micrographs that entire plates of
bainite can be imaged.
Vickers hardness tests are reported as the average of at
least ten tests. The tests were conducted using a 1 kg load,
each value represents the mean of those measurements.
and film-like retained austenite. Figure 3 shows the high
magnification TEM images of the specimens isothermally
held at 2008C. It is obvious that the thickness (33 nm) of
Alloy 2 was much smaller than that (47 nm) of the parent
Alloy 1, as shown in Figure 4. The measured hardness
(Figure 4) further confirmed the observed microstructures.
Alloy 2 with a finer microstructure had a higher hardness
than the parent Alloy 1. The hardness of both steels was
reduced when they were transformed at higher transform-
ation temperatures.

4. Results
4.1. Microstructures and Hardness

Representative SEM micrographs illustrating the micro-

structure of super bainitic steels with different compo-
sition are shown in Figure 2. It is seen that the
microstructures consist of extremely fine bainitic ferrite Figure 4. Thickness and hardness of super bainitic steels.

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Figure 5. a) Volume fraction and b) carbon concentration of phases in super bainitic steels.
4.2. Phase Fractions and Carbon Content
X-ray analysis show that the transformed microstructures
consist of bainitic ferrite and carbon-enriched retained
austenite (Figure 5). It is seen that the addition of Co
and Al increases the volume fraction of bainite and carbon
concentration of retained austenite (Figure 5). In addition,
for both steels, the volume fraction and carbon concen-
tration of retained austenite increases with the increase in
the transformation temperature.
5. Discussion
5.1. Microstructural Effects
The hardness versus the reciprocal of plate thickness and
volume fraction for bainite are plotted in Figure 6. It is seen
that the hardness increases with decreasing bainite plate
thickness and increases with increasing bainite volume
fraction. The increase in strength is due to the thinner
bainitic ferrite plates generated at lower temperatures.
Figure 6. Plot of a) hardness versus the reciprocal of plate thickness and b) hardness versus volume fraction of bainite.
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The contribution to strength due to the size of the plates
is given by Ds ¼ 115ðLÞ1 MPa where L is the mean linear
intercept in micrometers.[24] From this equation, and given
the very fine scale of the bainitic ferrite plate, it is easily
known that much of the strength of low-temperature bain-
ite is due to the fine scale plate. In practice, the mean lineal
intercept L should depend on the fraction of bainite (Vb ), if
plates are assumed to be square, then ðLÞ1 /Vb =t, since the
ferrite plates are dispersed in the austenite matrix.[24]
5.2. Incomplete Reaction
The carbon concentration in the retained austenite and
bainitic ferrite were determined using standard X-ray
analysis (Figure 5) for the samples in which the transform-
ation had stopped. The T0/ and the paraequilibrium a þ g/
g phase boundaries were calculated using MUCG83.Mod
program (Figure 7).[18] The effect of Co and Al addition on
the shifting of T0 curves were also calculated for the heat
treatment of bainitic steels. As the super bainitic trans-
formation proceeded, the carbon was expelled from the
bainite into the austenite. Due to the Co and Al addition,
the carbon content of the retained austenite increased and
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Figure 7. Calculated T0 curves for bainitic transformation and
the measured carbon content for Alloy 1 (open circles) and
Alloy 2 (solid circles).
eventually the bainitic transformation stopped when the
carbon content in austenite reached the T0 line. The pres-
ence of silicon prevents the complete transformation of
austenite because the reaction to bainite stops when the
chemical composition of the austenite violates the growth
condition.[25] Thus, the completion of transformation
leaves carbon-enriched retained austenite which can no
longer transform into bainite. It is seen that the measured
carbon concentration is below Ae3/ phase boundaries
that predict. As expected from the incomplete-reaction
phenomenon,[25] the carbon concentration of austenite
at the point where the reaction terminates is far less than
demanded by equilibrium (Ae3/), and close to that expected
from the T0/ phase boundary after allowing for the hetero-
geneous distribution of carbon.[25]
6. Conclusions
Low temperature nanostructured bainitic steels can be
designed theoretically on thermodynamics and kinetics
models. A mixed microstructure of extremely fine bainitic
ferrite plate and retained austenite was developed from
austenite by isothermal transformation at low tempera-
tures. The transformation of very strong nanostructured
bainite can be accelerated by the addition of Co and Al.
Acknowledgments
The authors gratefully acknowledge the financial support
from the International Science and Technology
Cooperation Program of China under Grant No.
S2012ZR0211. All authors are grateful to Prof. Harry
Bhadeshia for providing alloys.
Received: December 12, 2012
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Keywords: steels; microstructure; transformation;
hardness; super bainite
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