metals

Article
Influences of Alloying Elements on Continuous
Cooling Phase Transformation and Microstructures of
Extremely Fine Pearlite
Lulu Feng 1,2 , Feng Hu 1, *, Wen Zhou 1 , Rui Ke 1 , Guohong Zhang 1 , Kaiming Wu 1, * and
Wenwei Qiao 3
1 The State Key Laboratory for Refractories and Metallurgy, Hubei Collaborative Innovation Center on
Advanced Steels, International Research Institute for Steel Technology, Wuhan University of Science and
Technology, Wuhan 430081, China; fll85013296@163.com (L.F.); zw111zhou@163.com (W.Z.);
kerui428@sina.com (R.K.); zhangguohong@wust.edu.cn (G.Z.)
2 School of Mechanical Engineering, Jing Chu University of Technology, Jingmen 448000, China
3 Jiangsu Huaneng Cable Co., Ltd., Gaoyou 225613, China; chinamanxww@163.com
* Correspondence: hufenghf@126.com (F.H.); wukaiming@wust.edu.cn (K.W.); Tel.: +86-27-6886-2266 (F.H.);
+86-27-6886-2772 (K.W.)




Received: 27 December 2018; Accepted: 9 January 2019; Published: 11 January 2019


Abstract: In the present research, the cooling phase transformation characteristics and
microstructures of a Co- and Al-containing high-carbon steel were investigated under slow
cooling rates (0.02–2.0 ◦ C/s). In addition, by means of a Thermecmastor thermal simulator,
the phase transformation temperatures were measured, and the corresponding continuous cooling
transformation (CCT) curves were plotted. It was found that an extremely fine, fully pearlitic structure
with an interlamellar spacing of 45 nm, and a hardness of 425 HV1 (Vickers hardness under 1 kg
load) were obtained at a cooling rate of 0.1 ◦ C/s. The addition of Co and Al accelerated the pearlitic
reaction and reduced the interlamellar spacing by increasing the free energy of phase transformation,
thus a fully pearlitic structure was obtained at slow cooling rates.

Keywords: bridge cable steel; extremely fine pearlite; microstructure; hardness; slow cooling

1. Introduction
Ultra-high strength, super bainite steel was first developed by Bhadeshia et al. from The University
of Cambridge [1–4]. Low-temperature bainites obtained from the austenitization of super bainite steel
at low temperatures (125–300 ◦ C), possess super thin (thickness of 20–40 nm) bainite-ferrite strips and
carbon-rich retained austenites. The values of tensile strength, hardness, and fracture toughness of
super bainite steel are generally found as 1.7–2.2 GPa, 600 HV, and 30–40 MPa·m1/2 , respectively [5].
However, a very long isothermal transition time (sometimes two weeks) is generally required during
low-temperature bainite transformations [6]. Therefore, in order to accelerate the transformation of
low-temperature bainite isothermal transitions, Co and Al are usually added to improve the driving
force of the transformation [7], because Co and Al can increase the diffusion rate of carbon in austenite,
increase the temperature of transformation, and shorten the time of transformation. Adding Co and Al
to steel accelerates the bainitic transformation, shortens the austenite-to-bainite transformation time,
and refines grain of bainite [8].
Jaramillo et al. [9] were the first to completely austenitized a super bainitic steel (0.78 wt% C)
under 30 T super magnetic field and then cooled to room temperature at a cooling rate of 1 ◦ C/s,
to obtain an ultra-fine pearlite structure (lamella spacing of 50–100 nm). However, the synthesis of
bainitic steels under such high magnetic field (30 T) is very expensive and difficult in practice. Shi [10]

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Metals 2019, 9, 70 2 of 8

obtained an ultra-fine pearlitic structure (lamella spacing of 80–150 nm) during the transformation of
ultra-high carbon steel (1.5–2 wt% C) in the pearlite phase region. However, proeutectoid cementite
easily precipitated from austenite, and consequently, reticular carbide and graphite were formed.
Houin et al. [11] produced a full pearlite structure (lamella spacing of ~150 nm) from medium carbon
steel (0.4 wt% C), under super-fast cooling conditions (70–140 ◦ C/s); however, it is impossible to
achieve such a high cooling rate in practice.
Ultra-fine pearlitic structures can also be obtained after plastic deformation, including thermal
and non-thermal deformation treatments [12]. Sun et al. [13] found that the proportion of fine pearlite
lamella increased with the increasing rolling reductions; however, the manufacturing process was
complex and the production efficiency was low.
The role of Co and Al elements in bainitic steels were investigated by Garcia-Mateo and Caballero
et al. [4]. In the present work, we studied their role in pearlitic steels. Co and Al were added to
a high-carbon steel in order to increase the driving force of phase transformation, and to obtain
an ultra-fine fully pearlitic structure at slow cooling rates without any deformation treatment.
The extremely fine pearlite steel, not only has high strength (tensile strength up to 2000 MPa), but also
has good plasticity and toughness (torsion performance up to 24 times) [14]. It therefore has more
and more wide potential application in bar products, cable steels, etc., especially for the long-span
suspension and cable-stayed bridges, which are usually manufactured under slow cooling.

2. Materials and Methods

The alloy was prepared in a vacuum furnace (50 kg), all alloying material (including Co and Al)
was added to the smelting process, and the alloy was cast into ingots in the laboratory. The chemical
composition of the experimental steel is presented in Table 1, and Alloy 1 contained 3.87 wt% Co
and 1.37 wt% Al. The sample was first homogenized for two days at 1200 ◦ C in a vacuum annealing
furnace (Hengjin, Shenyang, China), and then cooled to room temperature (at cooling rates of 0.02 ◦ C/s,
0.05 ◦ C/s, 0.1 ◦ C/s, 0.5 ◦ C/s, 1 ◦ C/s, and 2 ◦ C/s) in order to obtain a full pearlite structure. The thermal
simulation sample (Ø8 mm × 12 mm) was obtained by the line cutting method. The thermal simulation
experiment was carried out using a Thermecmastor thermal simulator (Gleeble 3800, DSI, St. Paul,
DE, USA), whose maximum heating temperature was 1700 ◦ C. Both of the maximum heating and
cooling rates were 10,000 ◦ C/s, and the temperature precision was at ±1 ◦ C. The precise control of
temperature, time, and cooling speed was computerized. Moreover, the rate of temperature increase,
the austenitization temperature, and the holding time were set to 10 ◦ C/s, 1000 ◦ C, and 10 min,
respectively. The expansion parameters of the sample during heating (cooling) were measured by a
helium-neon laser, and the corresponding data were analyzed using the Origin 8.0 software (Origin
Lab, Northampton, MA, USA), in order to obtain the thermal expansion curves and the continuous
cooling transformation (CCT) curves.

Table 1. Chemical composition of the tested steels (wt%).

Alloys C Si Mn Mo Cr Co Al
Alloy 1 0.78 1.60 2.02 0.24 1.01 3.87 1.37
Alloy 2 0.79 1.59 1.94 0.30 1.33 - 0.01

Samples of the thermal simulation experiment were first ground by a SiO2 sandpaper,
then polished with a 2.5 µm diamond polishing agent, and finally, etched in a 4 vol% nitric alcohol
solution. The structures and the surface morphologies of the samples were analyzed by optical
microscopy (OM; Olympus BM51, Olympus Corporation, Tokyo, Japan), scanning electron microscopy
(SEM; Sirion 200, FEI, Hillsboro, OR, USA), and transmission electron microscopy (TEM; JEM–2010HT,
Hitachi, Ibaraki, Japan) techniques. The TEM sample were treated as follows: (1) cut into a thickness
of 0.3 mm by the linear cutting method; (2) ground to a thickness of 50–80 µm by the SiO2 sandpaper;
(3) punch out a small circle of 3 mm diameter on a special puncher; and finally (4) polish on an
Metals 2019, 9, 70 3 of 8
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loading,
MTP–1Aand type10electrolytic
points were measured to calculate
double-sprinkler the average
at a temperature ofvalue
20 ◦ Cand
andthe standardvoltage
a polishing deviation. The
of 70 V.
volume
loading, fraction
and4%
In addition, of pearlite
10 points was
wereacid
perchloric measured
measured using
to calculate
and anhydrous the standard
the average
ethanol were usedpoint
value counting
in and technique
the standard
the electrolytic [15], and
deviation. The
double-sprinkler.the
lamellar
volume
The spacing
fraction
Buchler’s ofpearlite
of pearlite
hardness wasmeasured
was calculated
measurement by the
using
test was linear
the
carried outintercept
standard method
point
for 20 1.0(Circular
counting
s under testand
kgtechnique
loading, line method)
[15],10and the
points
[16].
lamellar spacing of pearlite was calculated by the linear intercept method (Circular
were measured to calculate the average value and the standard deviation. The volume fraction of test line method)
[16].
pearlite was measured using the standard point counting technique [15], and the lamellar spacing of
3. Results
pearlite was calculated by the linear intercept method (Circular test line method) [16].
3. Results
3.1. Transformation Microstructure
3. Results
3.1. Transformation
Figure 1 displays Microstructure
the optical microstructures of Alloy 1 at different cooling rates. The complete
3.1. Transformation Microstructure
pearlite structure
Figure was the
1 displays obtained
opticalatmicrostructures
cooling rates less than 10.1
of Alloy at °C/s (Figure
different 1a). rates.
cooling Moreover, a mixed
The complete
structure
Figureof pearlite
1 displays (volume
the fraction
optical of 17 ± 6%)
microstructures andof martensite
Alloy 1 at was formed
different at
cooling
pearlite structure was obtained at cooling rates less than 0.1 °C/s (Figure 1a). Moreover, a mixed cooling
rates. rates
The less than
complete
0.5 °C/s (Figure 1b), and a complete martensite structure
thanwas ◦
0.1 formed at cooling ratesrates
higher than
pearlite
structure structure
of pearlite was obtained
(volume at cooling
fraction of 17 ± rates
6%) andlessmartensite C/s (Figure
was formed 1a).
at Moreover,
cooling than1
a mixed
less
°C/s (Figure
structure of 1c).
pearlite (volume fraction of 17 ± 6%) and martensite was formed
0.5 °C/s (Figure 1b), and a complete martensite structure was formed at cooling rates higher than at cooling rates less than1
0.5 ◦ C/s
Figure 2 exhibits
(Figure 1b), the
and aoptical
completemicrostructures
martensite of Alloy
structure 2
wasat different
formed at cooling
cooling rates.
rates A complete
higher than
°C/s (Figure 1c).
◦ C/s (Figure
1pearlite structure1c).was theobtained
Figure 2 exhibits opticalatmicrostructures
cooling rates less ofthan 0.05
Alloy °C/s
2 at (Figurecooling
different 2a). In rates.
addition, a mixed
A complete
pearlite structure was obtained at cooling rates less than 0.05 °C/s (Figure 2a). In addition, a(Figure
structure
Figure of 2pearlite
exhibits (78 ±
the 8%) and
optical martensite was
microstructures formed
of Alloy at
2 cooling
at rates
different less
cooling than 0.1
rates. °C/s
A complete
mixed
2b), andstructure
pearlite aofcomplete was martensite
obtained structure
at cooling was
ratesobtainedthanat0.05
lessformed ◦ C/srates
cooling higher
(Figure than
2a). than 0.5 °C/s
°C/sa(Figure
In addition, (Figure
mixed
structure pearlite (78 ± 8%) and martensite was at cooling rates less 0.1
2c).
structure
2b), and aofcomplete
pearlite (78 ± 8%) and
martensite martensite
structure waswas formedatatcooling
obtained cooling rates
rates less than
higher 0.1 ◦0.5
than C/s°C/s
(Figure 2b),
(Figure
and a complete martensite structure was obtained at cooling rates higher than 0.5 ◦ C/s (Figure 2c).
2c).

Figure 1. Optical micrographs of Alloy 1 at the cooling rates of (a) 0.1 °C/s, (b) 0.5 °C/s, and (c) 1.0
°C/s.
Figure
Figure 1. Optical micrographsofofAlloy
Optical micrographs Alloy 1 the
1 at at the cooling
cooling ratesrates (a)◦ C/s,
of (a)of0.1 0.1 °C/s, (b)◦ C/s,
(b) 0.5 0.5 °C/s, and
and (c) ◦ C/s.
1.0(c) 1.0
°C/s.

Figure 2. Optical micrographs of Alloy 2 at the cooling rates of (a) 0.05 ◦ C/s, (b) 0.1 ◦ C/s, and (c) 0.5 ◦ C/s.
Figure 2. Optical micrographs of Alloy 2 at the cooling rates of (a) 0.05 °C/s, (b) 0.1 °C/s, and (c) 0.5
°C/s. 2.Expansion
3.2. Thermal
Figure and CCT Curves
Optical micrographs of Alloy 2 at the cooling rates of (a) 0.05 °C/s, (b) 0.1 °C/s, and (c) 0.5
°C/s.
A spinodal
3.2. Thermal point appeared
Expansion in the expansion curve during continuous cooling from austenitization
and CCT Curves
to room temperatures. The relationship between the linear expansion of steel and temperature at
3.2. Thermal Expansion and appeared
CCT Curvesin the expansion curve during continuous cooling from
0.02 ◦AC/sspinodal
and 0.2 ◦ point
C/s cooling rates was obtained by a thermal simulator (Figure 3). It is evident that
austenitization
under A the sameto
spinodal room conditions,
point
cooling temperatures.
appeared Alloy in The
the1 relationship
expansion abetween
manifested curve the linear
higherduring expansion
continuous
transformation of steeland
cooling
temperature and
from a
temperature
austenitization at 0.02
to °C/s
room and 0.2 °C/s
temperatures. cooling
The rates was
relationship obtained
between by a
the thermal
linear
shorter transformation time compared to Alloy 2. Based on the temperature–expansion curves, the simulator
expansion (Figure
of steel 3).
and It
is evident
temperature
starting that under
at 0.02
temperatures, °C/sthe
the same
andending
0.2 °C/scooling
coolingconditions,
temperatures, was Alloy
rates and obtained
the 1 manifested
by a thermal
transformation a simulator
higher
times transformation
(Figure
at different 3). It
cooling
temperature
is evident
rates and a
that underand
were measured, shorter
thethetransformation
same
CCTcooling time compared
conditions,
curves were plottedAlloy to Alloy
based 1onmanifested 2.
the obtainedBased on the
a temperature temperature–
higher transformation
points and
expansion
temperature
holding timescurves,
and athe
of pearlitestarting
shorter and temperatures,
transformation
martensite. The the
timeCCTending
compared
curvestemperatures,
oftothe
Alloy 2.and the on
Based
experimental transformation
theare
steels times
temperature–
depicted in
at different
expansion cooling
curves,
Figure 4. These rates
theshow
data were
starting measured,
thattemperatures,
the starting andand the
thethe CCT
ending
ending curves were
temperatures,
temperaturesand plotted based
theperlite
of the on the
transformation obtained
times
transformation
temperature
at
significantly points
different cooling and
ratesholding
increased, were
and times
themeasured, of pearlite
and the
transformation and martensite.
CCT
time curves were
remarkably The CCT curves
plotted
decreased dueoftothe
based theexperimental
on the obtained
addition of
steels are
temperature depicted
points in
andFigure 4.
holding These
times data
of show
pearlite that
and the starting
martensite. and
The the
CCT
3.87 wt% Co and 1.37 wt% Al. For example, in the case of Alloy 1, at a cooling rate of 0.1 C/s ending
curves temperatures
of the of◦
experimental the
perliteare
steels transformation
depicted in Figuresignificantly
4. These increased,
data show and thethe
that transformation
starting and time remarkably
the ending decreased
temperatures of due
the
to the addition
perlite of 3.87 significantly
transformation wt% Co and increased,
1.37 wt% Al. andFor
theexample, in the case
transformation timeof Alloy 1, atdecreased
remarkably a cooling duerate
to the addition of 3.87 wt% Co and 1.37 wt% Al. For example, in the case of Alloy 1, at a cooling rate
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2019, 8, 70FOR PEER REVIEW 44of
of 88
of Metals
0.1 °C/s and pearlite transformation starting and ending temperatures of 683 °C and 661 °C,
of 0.1 °C/s and
respectively, the pearlite transformation
transformation holdingstarting
time was and 198
ending temperatures
s; whereas of 6832,°Cthe
for Alloy andpearlite
661 °C,
of 0.1 °C/s and
respectively, the pearlite transformation
transformation holding starting
time and 198
was endings; temperatures
whereas ◦for of 683 2,
Alloy ◦°Cthe
andpearlite
661 °C,
transformation starting and ending
and pearlite transformation temperatures
starting and endingwere 673 °C and
temperatures 629 °C,
of 683 respectively,
C and and the
661 C, respectively,
respectively, the
transformation transformation
starting andincreased
ending holding time was 198
673 s;°C2,whereas
629 for Alloy 2, the and
pearlite
transformation holding
the transformation time
holding time wastemperatures
to198
235s; s.whereas were
for Alloy and °C,transformation
the pearlite respectively, the
starting
transformation
transformation starting
holding timeand ending
increased temperatures were 673 °C and 629 °C, respectively, and the
and ending temperatures were 673 ◦ C to 235629
and s. ◦ C, respectively, and the transformation holding time
transformation holding time increased to 235 s.
increased to 235 s.

Figure 3. Dilatational strain as a function of temperature: (a) Alloy 1, and (b) Alloy 2.
Figure
Figure3.3.Dilatational
Dilatationalstrain
strainasasa afunction
functionofoftemperature:
temperature:(a)
(a)Alloy
Alloy1,1,and
and(b)
(b)Alloy
Alloy2.2.
Figure 3. Dilatational strain as a function of temperature: (a) Alloy 1, and (b) Alloy 2.

Figure 4. The
Figure CCTCCT
4. The (Continuous Cooling
(Continuous Transition)
Cooling curves
Transition) of the
curves oftested steels:steels:
the tested (a) Alloy 1 and 1(b)
(a) Alloy and
Figure
Alloy 2. 4. The CCT (Continuous Cooling Transition) curves of the tested steels: (a) Alloy 1 and (b)
(b) Alloy 2.
Figure
Alloy 2. 4. The CCT (Continuous Cooling Transition) curves of the tested steels: (a) Alloy 1 and (b)
3.3.3.3. Alloy
Lamellar
Lamellar 2. Spacing
Spacing andand Hardness
Hardness of the
of the Pearlite.
Pearlite.
3.3. Lamellar Spacing and Hardness of the Pearlite.
The
3.3.The morphology
morphology
Lamellar of of
Spacing and pearlite
pearlite
Hardness ofstructure
structure was was
the Pearlite. studied
studied using
using SEMSEM (Figure
(Figure 5),5),
and and thethe results
results of of
The
lamellar morphology
spacing and of pearlite
hardness ofstructure
pearlite was
are studied
presented using
in SEM
Table 2 (Figure
and
lamellar spacing and hardness of pearlite are presented in Table 2 and Figure 6. At a cooling rate ofFigure5), and
6. At the
a results
cooling of
rate
The
lamellar ◦ morphology
spacing and of pearlite
hardness of structure
pearlite are was studied
presented in using
Table SEM
2 and (Figure
Figure 5),
6. Atanda the
cooling results
rate ofof
0.1of°C/s,
0.1 Alloy
C/s, Alloy 1 yielded
1 yielded an ultrafine
an ultrafine pearlite
pearlite structure,
structure, with with a lamellar
a lamellar spacingspacing
of 45ofnm 45 and
nm and
a
lamellar
0.1 °C/s,
a hardness spacing
Alloy 1
ofHV1.and hardness
yielded
425 HV1. an of pearlite
ultrafine
However, are
pearlite
when presented
structure,
the cooling in Table
with a 2 and
lamellar Figure 6.
spacing At
◦ ofa cooling
45 nm rate
and of
a
hardness of 425 However, when the cooling rate wasrate was reduced
reduced to 0.02 °C/s,to 0.02
the valueC/s, ofthe value of
lamellar
0.1 °C/s,of
hardness
lamellar Alloy
425
spacing 1 increased
HV1.yielded antoultrafine
However, when
95 nm, the
andpearlite
cooling
the structure,
rate
value was
of with adecreased
reduced
hardness lamellar
to 0.02 spacing
°C/s,
to the
355 of 45of
value
HV1. Innm and a
lamellar
contrast,
spacing increased to 95 nm, and the value of hardness decreased to 355 HV1. In contrast, Alloy 2
hardness
spacing
Alloy of 425 HV1.
2 increased
manifested 95However,
tolargernm, and when
lamellar the the cooling
value
spacings of rate
hardness
(80–130 nm)was reduced
decreased
and smaller totohardness
0.02HV1.
355 °C/s,values
thecontrast,
In value of Alloy
(310–400 lamellar
HV1).2
manifested larger lamellar spacings (80–130 nm) and smaller hardness values (310–400 HV1).
spacing
manifested
Therefore, increased
larger to 95
lamellarnm, and
spacingsthe value of
(80–130 nm) hardness decreased
and the
smaller to 355
hardness HV1.
values In contrast,
(310–400 Alloy
HV1).2
Therefore, thethe addition
addition of of
CoCoand and
AlAl significantly
significantly reduced
reduced the lamellar
lamellar spacing
spacing and and simultaneously,
simultaneously,
manifested
Therefore,
increased thelarger lamellar
addition of
microstructure Co spacings (80–130 nm) and smaller hardness values
and Al significantly reduced the lamellar spacing and simultaneously,
hardness. (310–400 HV1).
increased microstructure hardness.
Therefore,
increased the addition of
microstructure Co and Al significantly reduced the lamellar spacing and simultaneously,
hardness.
increased microstructure hardness.

Figure 5. SEM (Scanning Electron Microscope) micrographs of the tested steels at a cooling rate of
Figure◦ 5. SEM (Scanning Electron Microscope) micrographs of the tested steels at a cooling rate of 0.1
0.1 C/s;
Figure (a) Alloy
5. SEM 1, andElectron
(b) Alloy 2.
°C/s; (a) Alloy 1,(Scanning
and (b) Alloy 2. Microscope) micrographs of the tested steels at a cooling rate of 0.1
Figure 5. SEM (Scanning Electron
°C/s; (a) Alloy 1, and (b) Alloy 2. Microscope) micrographs of the tested steels at a cooling rate of 0.1
°C/s; (a) Alloy 1, and (b) Alloy 2.
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Table 2. Relationship between cooling rate and lamellar spacing or hardness.

Table 2. Relationship between

Sample cooling
Alloy 1 rate and lamellar spacing orAlloy
hardness.
2
Cooling Rate,
Sample
°C/s 0.02 0.05
Alloy 1
0.1 0.02 0.05
Alloy 2
0.1
Interlamellar Spacing,
Cooling Rate, ◦ C/s 95 ± 15
0.02 65 ±0.05
10 45 ±0.1
10 1300.02
± 15 100
0.05 ± 15 80 ± 10
0.1
nm Spacing, nm
Interlamellar 95 ± 15 65 ± 10 45 ± 10 130 ± 15 100 ± 15 80 ± 10
Hardness,
Hardness, HV1HV1 355355 ± 10 375375
± 10 ± 10 425
± 10 425±± 310 ±
1010 310 10
± 10 340
340± 10 ± 10± 10
± 10 400400

Figure 6.
Figure The phase
6. The phase fraction
fraction and
and hardness
hardness of
of the
the tested
tested steels
steels at
at different
different cooling
cooling rates.
rates.

4. Discussion
4. Discussion
4.1. Effects of Co and Al on the Structure and Lamellar Spacing of Pearlite
4.1. Effects of Co and Al on the Structure and Lamellar Spacing of Pearlite
Figure 7 illustrates the effects of 3.87 wt% Co and 1.37 wt% Al on the time temperature
Figure 7 illustrates the effects of 3.87 wt% Co and 1.37 wt% Al on the time temperature
transformation (TTT) curve, and free energy driving force (calculated by MUCG 83.Mod software [17])
transformation (TTT) curve, and free energy driving force (calculated by MUCG 83.Mod software
of the experimental steel. Figure 7a shows that the addition of Co and Al increased the temperature
[17]) of the experimental steel. Figure 7a shows that the addition of Co and Al increased the
of the pearlite transformation, shifted the C curve left, and shortened the duration of the pearlite
temperature of the pearlite transformation, shifted the C curve left, and shortened the duration of the
transformation. Moreover, Co and Al increased the diffusion rate of carbon in austenite, accelerated
pearlite transformation. Moreover, Co and Al increased the diffusion rate of carbon in austenite,
the pearlite transformation, increased the eutectoid transformation temperature, and increased the
accelerated the pearlite transformation, increased the eutectoid transformation temperature, and
supercooling degree. Takahashi [18] developed a model based on the relationship between the lamellar
increased the supercooling degree. Takahashi [18] developed a model based on the relationship
spacing of pearlite and the supercooling degree after applying the eutectoid transformation.
between the lamellar spacing of pearlite and the supercooling degree after applying the eutectoid
transformation. T −T ∆T
log S0 = a − b log( E ) = a − b log( )
TE T
TE − T ΔT E
log S0 = a − b log( ) = a − b log( )
where S0 denotes pearlite lamellar spacing, TE is the TE eutectoid transformation
TE temperature, and ∆T
signifies the supercooling degree. It is discernible that smaller lamellar spacings were obtained
where S0 denotes pearlite lamellar spacing, TE is the eutectoid transformation temperature, and
at higher supercooling degrees; therefore, Co and Al significantly reduced the lamellar spacing of
ΔT signifies
pearlite. the supercooling
Consequently, shorterdegree. It is discernible
dislocation that during
slips occurred smallerplastic
lamellar spacings were
deformation, obtained
resulting in
at higher supercooling degrees; therefore, Co and Al significantly reduced the lamellar
higher hardness values of pearlite structures. Capdevila et al. [19] employed a neural network model spacing of
pearlite.
to evaluateConsequently,
the effects ofshorter dislocation
different slips occurred
alloy elements during
on lamellar plasticofdeformation,
spacing pearlite, andresulting
found thatin
higher
austenitehardness values
stabilizing of pearlite
elements, structures.
such as Mn, Cr, Capdevila
Ni, andetMo,al. [19] employedincreased
significantly a neural network model
the spacing of
to evaluate the effects of different alloy elements on lamellar spacing of pearlite,
pearlite lamellae; however, the stable elements of ferrite, such as Co and Al, reduced the spacing and found that
of
austenite stabilizing
pearlite lamellae. elements, such as Mn, Cr, Ni, and Mo, significantly increased the spacing of
pearlite lamellae; however, the stable elements of ferrite, such as Co and Al, reduced the spacing of
pearlite lamellae.
Metals 2019, 9, 70 6 of 8
Metals 2018, 8, x FOR PEER REVIEW 6 of 8

Metals 2018, 8, x FOR PEER REVIEW 6 of 8

Effect of
Figure 7. Effect of Co
Co and
and Al
Al addition
addition on
on phase
phase transformation;
transformation; (a)
(a) the
the shifting
shifting of
of TTT
TTT (Time,
(Time,
Temperature,
Temperature, Transformation)
Transformation)curves,
curves,and
and(b)
(b)the
thefree
freeenergy
energychange.
change.

Figure
4.2. Effects of Co7. Effect
and Alofon CoKinetics
and Al and
addition on phase transformation;
Thermodynamics of the Pearlite (a) the shifting of TTT (Time,
Transformation
4.2. Effects of Co and Al on Kinetics and Thermodynamics of the Pearlite Transformation
Temperature, Transformation) curves, and (b) the free energy change.
For Alloy 1, the SEM image after isothermal treatment and TEM image for the cooling rate of
◦
For Alloy 1, the SEM image after isothermal treatment and TEM image for the cooling rate of 0.1
0.14.2.
C/sEffects
are of Co and Al on
displayed in Kinetics
Figuresand Thermodynamics
8 and 9, respectively. of theAlthough
Pearlite Transformation
the carbon content in Alloy 1 was
°C/s are displayed in Figures 8 and 9, respectively. Although the carbon content in Alloy 1 was 0.78
0.78 wt%, it remained hypoeutectoid steel due to the addition of Co and Al.cooling
For example, Alloy 1
wt%, it For Alloy 1,hypoeutectoid
remained the SEM image after steelisothermal
due to thetreatment
additionand of Co TEM andimage for the
Al. For
◦ C for 30 min, then heated at 700 ◦ C for 5 h, and finally quenched in water
example, rate of 10.1
Alloy was first
was°C/s
first heated at 1000
heated are displayed
at 1000 °C for in 30
Figures
min,8thenand 9, respectively.
heated at 700 Although
°C for 5 h, theand carbon content
finally in Alloyin
quenched 1 was
water 0.78to room
to room
wt%, ittemperature.
remained Consequently,
hypoeutectoid steel duea tomartensite
the addition structure
of Co and with
Al. a small
For example, amount
Alloy 1ofwasproeutectoid
first
temperature. Consequently, a martensite structure with a small amount of proeutectoid ferrite was
heated
ferrite was at 1000 °C for[20,21],
obtained 30 min, then
which heated
wereat intimately
700 °C for 5connected
h, and finally quenched
with in water or
the complete to room
incomplete
obtained [20,21], which were intimately connected with the complete or incomplete wetting of grain
temperature. Consequently, a martensite structure with a
wetting of grain boundaries by the second solid phase, proeutectoid ferrite was obtained small amount of proeutectoid ferrite was in case
boundaries by the second solid phase, proeutectoid ferrite was obtained in case of high amount of a
obtained [20,21], which were intimately connected with the complete
of high amount of a wetting phase [22,23]. Generally, a complete pearlite structure can be obtained in or incomplete wetting of grain
wetting
boundariesphaseby [22,23]. Generally,
the second a complete
solid phase, pearlite
proeutectoid structure
ferrite was obtainedcan be in obtained
case of highin hypoeutectoid
amount of a steel
hypoeutectoid steel at higher cooling rates. For example, a complete pearlite structure can be obtained
at wetting
higher phase cooling rates.
[22,23]. For example,
Generally, a complete a complete pearlitecan
pearlite structure structure
be obtained can◦inbe obtained in
hypoeutectoid Fe–0.4C–
steel
in Fe–0.4C–0.62Mn–0.30Si–0.024Al (in wt%) alloy at a cooling rate of 140 C/s [11]. It is evident from
0.62Mn–0.30Si–0.024Al
at higher cooling rates.(in Forwt%) alloy aatcomplete
example, a cooling rate of
pearlite 140 °C/s
structure can[11]. It is evident
be obtained from the free
in Fe–0.4C–
the0.62Mn–0.30Si–0.024Al
free energy curve in Figure 7b,alloy
that atCoa and Al significantly increased theevident
free energy of austenite to
energy curve in Figure (in 7b,wt%)
that Co and Al significantly
cooling rate of 140increased
°C/s [11]. the It is free energyfromof theaustenite
free to
pearlite
energytransformation.
curve in Figure PearlitePearlite transformation
7b, that transformation
Co and Al significantly is a local equilibrium
increased the free phase
energy transformation process;
of austenite toprocess;
pearlite transformation. is a local equilibrium phase transformation
therefore,
pearlite the increase
transformation. in the transformation’s
Pearlite transformation driving
is a local force
equilibrium can
therefore, the increase in the transformation’s driving force can be attributed to the transformation be attributed
phase to
transformation the transformation
process;
from
from aa system’s
system’s
therefore, para-equilibrium
the increase totoequilibrium
in the transformation’s
para-equilibrium equilibrium
driving[24].[24].
force
Hence, Hence,
can be during
attributed
during the to thethe transformation
transformation
transformation from
from para-
from a system’s
para-equilibrium para-equilibrium
to equilibrium, to equilibrium
precipitation [24]. Hence,
ofcementite
fine cementite during canthe transformation
be obtained from para-
equilibrium to equilibrium, precipitation of fine can be obtained [24]. [24].
equilibrium
Hultgrentoand equilibrium,
Honeycombe precipitation of fine cementite
[25] published that can by be obtained [24].
extending the local region of γ + θ/γ
Hultgren and Honeycombe [25] published that by extending the local region of γ + θ / γ phase
phase or Hultgren
α + γ/γ andphase
Honeycombe [25] published
in a low-carbon orthat by extending the
hypoeutectoid local
steel, it region of γ + θto/ γtransform
is possible phase the
α +αγ+/γγ/ γ phase
or or phase ininaa low-carbon
low-carbon orhypoeutectoid
or hypoeutectoid steel,
steel, it isitpossible
is possibleto to transform
transform the the austenite
austenite
austenite structure into fully pearlite structure when the transformation temperature is lower than the
structure
structureinto
equilibrium into fully
fully pearlite
eutectoid pearlite structure
structure
temperature. This when
when thethe
process transformation
transformation
requires temperature
a verytemperature
high cooling is rate
lowerisinlower
than
orderthe than the
to avoid
equilibrium
theequilibrium eutectoid
formation eutectoid temperature.
of proeutectoidtemperature.
ferrite. This
This process
Coprocess requires
and Alrequires a very
a very increase
significantly high
high cooling cooling rate
rate in order
the chemical in order
to avoid
driving to avoid
force and
thethe formationofofproeutectoid
formation proeutectoid ferrite.
ferrite. CoCo and
and AlAlsignificantly
significantly increase
increasethe chemical
the driving
chemical force and
driving force and
inhibit the formation of proeutectoid ferrite during para-equilibrium to equilibrium transformations.
inhibit
inhibit the the formationof
formation ofproeutectoid
proeutectoid ferrite
ferrite during
during para-equilibrium
para-equilibrium to equilibrium
to equilibriumtransformations.
transformations.
An extremely fine layer of cementite (Figure 9a) or a granular structure of cementite (Figure 9b) was
AnAn extremelyfine
extremely
formed at atvery
finelayer
layer ofof cementite
cementite (Figure
(Figure 9a)
9a)or or
a granular
a granular structure
structureof cementite
ofrate (Figure
cementite 9b) was
0.1 ◦(Figure
C/s). 9b) was
formed veryslowslowcooling
cooling rates (both
rates (both ofofthem
them were
were formed
formed at aat a cooling
cooling rate of 0.1of°C/s).
formed at very slow cooling rates (both of them were formed at a cooling rate of 0.1 °C/s).

Figure 8. 8.SEM
Figure SEMmicrographs of Alloy
micrographs of Alloy11that
thatconsists
consists of martensite
of martensite and and a little
a little allotriomorphic
allotriomorphic ferrite ferrite
(Specimen was austenitized at 1000 ◦ C for 30 min, then isothermally transformed at 700 ◦ C for 5 h,
(Specimen was austenitized at 1000 °C for 30 min, then isothermally transformed at 700 °C for 5 h,
Figure
before 8.being
before SEM
being micrographs
quenched
quenched into ofwater
the
into the Alloyatat
water 1room
that
room consists of martensite
temperature).
temperature). (a) 1000
(a) 1000 and a littletimes
magnification
magnification allotriomorphic
times
and, (b)and, ferrite
4000(b) 4000
(Specimen
magnification was austenitized
magnificationtimes.
times. at 1000 °C for 30 min, then isothermally transformed at 700 °C for 5 h,
before being quenched into the water at room temperature). (a) 1000 magnification times and, (b) 4000
magnification times.
Metals 2019, 9, 70 7 of 8
Metals 2018, 8, x FOR PEER REVIEW 7 of 8

TEMmicrographs
micrographsofofAlloy
Alloy1 1atata acooling
coolingrate
rateofof0.10.1 ◦ C/s; (a) cementite lamellae, and
Figure 9. TEM °C/s; (a) cementite lamellae, and (b)
(b) cementite
cementite particle.
particle.

5. Conclusions
5. Conclusions
In the present paper, the microstructures and hardness of a Co- and Al-containing high-carbon
In the present paper, the microstructures and hardness of a◦ Co- and Al-containing high-carbon
steel were investigated under slow cooling rates (0.02–2.0 C/s). Moreover, by means of a
steel were investigated under slow cooling rates (0.02–2.0 °C/s). Moreover, by means of a
Thermecmastor thermal simulator and metallographic-hardness test method, the corresponding
Thermecmastor thermal simulator and metallographic-hardness test method, the corresponding
continuous cooling transformation (CCT) curves were plotted.
continuous cooling transformation (CCT) curves were plotted.
(1) In comparison to conventional high-carbon steel, the experimental steel (3.87 wt% Co and
(1) In comparison to conventional high-carbon steel, the experimental steel (3.87 wt% Co and
1.37 wt% Al) increased the pearlite transformation temperature and shortened the transition time
1.37 wt% Al) increased the pearlite transformation temperature and shortened the transition time
under cooling rates of 0.02–0.1 ◦ C/s (for example, at 0.1 ◦ C/s cooling rate, the temperature increased
under cooling rates of 0.02–0.1 °C/s (for example, at 0.1 °C/s cooling rate, the temperature increased
from 673 ◦ C to 683 ◦ C, and the reaction time decreased from 235 s to 198 s). Therefore, the addition
from 673 °C to 683 °C, and the reaction time decreased from 235 s to 198 s). Therefore, the addition of
of Co and Al increased the driving force of austenite to pearlite transformation and accelerated the
Co and Al increased the driving force of austenite to pearlite transformation and accelerated the
pearlite transformation.
pearlite transformation.
(2) In comparison to conventional high-carbon steel, the experimental steel yielded an extremely
(2) In comparison to conventional high-carbon steel, the experimental steel yielded an extremely
fine pearlitic structure with an interlamellar spacing of 45 nm and a hardness of 425 HV1, under slow
fine pearlitic structure with an interlamellar spacing of 45 nm and a hardness of 425 HV1, under slow
cooling rates.
cooling rates. Therefore,
Therefore, the
the addition
addition of
of Co
Co and
and Al
Al significantly
significantly reduced
reduced the
the lamellar
lamellar spacing.
spacing.
Author Contributions: Literature search, L.F., W.Z. and R.K.; Figures, L.F. and R.K.; Study Design, L.F., G.Z., K.W.
Author
and W.Q.;Contributions: Literature
Data Collection, search,
L.F.; Data L.F.,L.F.,
Analysis, W.Z. andW.Z.,
F.H., R.K.;R.K.
Figures, L.F. and
and K.W.; DataR.K.; Study Design,
Interpretation, F.H., L.F.,
W.Z.,G.Z.,
G.Z.
K.W. and W.Q.;
and K.W.; Data
Writing, Collection,
L.F.; L.F.; Data Analysis,
Article Modification, F.H., W.Z.,L.F., F.H.,
G.Z. andW.Z.,
K.W.;R.K. and K.W.;
Funding DataK.W.
Support, Interpretation,
and W.Q. F.H.,
W.Z., G.Z. and K.W.; Writing, L.F.; Article Modification, F.H., W.Z., G.Z. and K.W.; Funding Support, K.W and
Funding: The authors sincerely thank the support from the National Key Research and Development Program
W.Q.
of China (No. 2017YFB0304800), the Major Technology Innovation of Hubei Province (No. 2016AAA022), the
Hubei Provincial Natural Science Foundation of Innovation Team (No. 2016CFA004), the National Natural Science
Funding: The authors sincerely thank the support from the National Key Research and Development Program
Foundation of China (NSFC) (No. 1532268; 51601134; 51671149), the Jingmen Science and Technology Planning
of China
Project (No.
(No. 2017YFB0304800),
2018YFYB054) the111
and the Major Technology Innovation of Hubei Province (No. 2016AAA022), the
Project.
Hubei Provincial Natural Science Foundation of Innovation Team (No. 2016CFA004), the National Natural
Conflicts of Interest: The authors declare no conflict of interest.
Science Foundation of China (NSFC) (No. 1532268; 51601134; 51671149), the Jingmen Science and Technology
Planning Project (No. 2018YFYB054) and the 111 Project.
References
Conflicts of Interest: The authors declare no conflicts of interest.
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