metals

Article
Effect of Tempering Temperature on the Low
Temperature Impact Toughness of 42CrMo4-V Steel
Chen Sun 1,2 , Pai-Xian Fu 1,2, *, Hong-Wei Liu 1,2 , Hang-Hang Liu 1,2 and Ning-Yu Du 1,2
1 Institute of Metal Research, Chinese Academy of Sciences, 72 Wenhua Road, Shenyang 110016, China;
csun15s@imr.ac.cn (C.S.); hwliu@imr.ac.cn (H.-W.L.); hhliu15b@imr.ac.cn (H.-H.L.);
nydu16s@imr.ac.cn (N.-Y.D.)
2 School of Materials Science and Engineering, University of Science and Technology of China,
72 Wenhua Road, Shenyang 110016, China
* Correspondence: pxfu@imr.ac.cn; Tel.: +86-242-397-1973




Received: 7 March 2018; Accepted: 29 March 2018; Published: 2 April 2018


Abstract: Effects of tempering temperature on the microstructures and low temperature impact
toughness of 42CrMo4-V steel were investigated. Microstructures of 42CrMo4-V steel after tempering
at 570–720 ◦ C for 3 h were experimentally investigated using scanning electron microscopy (SEM),
electron back-scattered diffraction (EBSD), transmission electron microscopy (TEM) and X-ray
diffraction (XRD). The results showed that the carbide precipitation sequence of 42CrMo4-V steel is
M8 C7 → M3 C and the absorbed energies of 42CrMo4-V steel increase greatly from 21.7 J to 132.3 J
with increasing tempering temperature from 570 ◦ C to 720 ◦ C. The changes of impact toughness with
increasing tempering temperature were attributed to the softening of matrix, the evolution of carbide
precipitates and grain structures.

Keywords: 42CrMo4-V steel; vanadium; tempering temperature; carbide precipitates; low

temperature impact toughness

1. Introduction
AISI 4140 or 42CrMo4 is a low-alloy structural steel widely used in important structural
components such as generator spindle, crane weight-on-wheel, automotive crankshafts [1], oil drill
pipe joints of deepwell, armour materials [2] and other applications [3,4].
42CrMo4 steel has attracted great attention due to its high strength and toughness, an interesting
fatigue behavior and good machinability [5–7]. Fatigue behavior was the most popular research
direction. Various factors such as heat treatment [8], environmental temperature [9], residual stress [10]
and chemical element [11] were taken into consideration towards improving fatigue performance of
the material. Surface treatment [12] and wear resistance [13] were another two focusing issues. Surface
nitriding treatment and laser surface hardening were still the main directions to improve the wear
resistance of tool steel. In addition, strengthening measures, welding performances and corrosion
protection treatments were also studied in published researches.
42CrMo4 steels was one of the main manufacturing steel for the main shaft of wind generators.
The main shaft is required to work at a low temperature in safe and reliable service conditions for
more than 20 years [14]. Meanwhile, the main shaft will be experience tensile, bending and shear
stresses as well as varying extreme weather conditions [15]. Therefore, a preferable low temperature
impact toughness was necessary for the main shaft that worked in cold weather. For most parts
of China, the coldest temperature needs to be set at −30 ◦ C in order to guarantee safe operation of
the wind generator. However, low temperature impact toughness, especially at −30 ◦ C or below,
was rarely reported.

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Metals 2018, 8, 232 2 of 12

With the development of wind generator operated at low temperature and at large size,
the adjustment of heat treatment alone was unsuccessful in producing 42CrMo4 steel that could satisfy the
requirement of the main shaft, so the optimization of chemical composition was necessary. The vanadium
element could refine grain size significantly, while also enabling formation of tiny V(C, N) particles
that prevent crack propagation [16,17]. In addition, the grain refinement effect of vanadium as well
as the formation of V(C, N) particles also have an important influence on the ductile-brittle transition
temperature [18,19]. Therefore, a moderate addition of vanadium could improve both strength and
toughness. Our group developed the 42CrMo4-V steel by adding an appropriate amount vanadium,
and hoping that would obtain a favorable low temperature impact toughness to meet the challenges.
Vanadium was a strong carbide forming element, so the addition of vanadium could have
an influence on the precipitation of carbides. Besides, the optimization of chemical composition
always led to the adjustment of heat treatment system. In the production processes of the main shaft,
tempering is the key process to improve toughness. In order to promote the industrial application
of 42CrMo4-V steel, it is necessary to clarify the relationship between its low temperature impact
toughness and tempering temperature. Thus, the present work has been aimed to evaluate the carbide
precipitates and low temperature impact toughness of the 42CrMo4-V steel subjected to tempered at
various temperature.

2. Experimental Procedures
The 42CrMo4-V steel used in this investigation was smelted in an electric furnace and refined
through a procedure of ladle furnace (LF), vacuum degassing furnace (VD). Then the ingot was forged
into a stepped shaft. Specimens with dimensions of 60 mm × 60 mm × 60 mm were taken from
the shaft, and the chemical composition is given in Table 1. The heat treatment process included
normalizing, quenching, and tempering. The normalizing temperature was selected to be 840 ◦ C for
3 h, followed by air cooling. The quenching temperature was 860 ◦ C for 3 h followed by water cooling.
Then, the tempering was performed at 570, 600, 630, 660, 690 and 720 ◦ C for 3 h followed by air cooling.

Table 1. Chemical compositions of 42CrMo4-V steel and traditional 42CrMo4 steel (wt. %).

Alloy C Si Mn Cr Mo S P Ni V
42CrMo4-V 0.40 0.25 0.73 1.12 0.26 0.0001 0.010 0.53 0.19
42CrMo4 0.38–0.45 0.17–0.37 0.50–0.80 0.90–1.20 0.15–0.25 ≤0.035 ≤0.035 - -

The microstructures of the tempered samples were observed by scanning electron microscopy
(SEM, S-3400N, Hitachi Company, Tokyo, Japan) and transmission electron microscopy (TEM, Tecmai
G2 20, FEI Company, Hillsboro, OR, USA). SEM specimens were polished and etched with 4 vol. %
nital solution. TEM samples were firstly made into 3 mm in diameter and 50 µm in thickness, and
then were electropolished by using a solution with 10 vol. % perchloric acid and 90 vol. % alcohol at a
voltage of 25 V and a temperature ranging between −30 ◦ C and −20 ◦ C. The grain orientations were
observed by Electron-backscattered diffraction (EBSD) with a step size of 0.5 µm. Only the results with
a hit rate more than 90% were used. The surface stress of EBSD samples was removed by ion etching
at a voltage of 3.5 kV, a current of 1.5 mA and an angle of 15◦ .
The precipitates were characterized using X-ray diffraction (XRD, D/Max-2500PC, Rigaku
Company, Tokyo, Japan) with Cu-Kα (λ = 1.5406 Å) with a scanning angle from 40◦ to 100◦ and
a scanning speed of 2◦ /min. And carbide powder for the XRD tests was extracted by using a solution
with 10 vol. % hydrochloric acid and 90 vol. % methanol.
Charpy V-notch specimens with gauge size of 10 mm × 10 mm × 55 mm were conducted on
RKP450 (Zwick-Roell Company, Ulm, Germany)impact testing machine using a 300 J hammer at
−30 ◦ C. Three experiments were conducted on each test condition. And then, the fracture surfaces
were characterized by SEM (S-3400N).
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3. Results and Discussion
3. Results and Discussion
3.1. Microstructures
3.1. Microstructures
Figure 1 shows the SEM microstructures of 42CrMo4-V steel tempered at different temperatures,
indicatingFigure
that martensite
1 shows thelaths are gradually recovered
SEM microstructures of 42CrMo4-V withsteel
increasing
temperedtempering
at differenttemperature.
temperatures, TEM
indicating that martensite laths are gradually recovered with increasing tempering temperature.
micrographs reflect this trend more clearly, as shown in Figure 2. The martensite TEM
lath boundaries
remainmicrographs reflect
intact after this trend
being more clearly,
tempered at 570as shown
◦ in Figure
C (Figure 2a). 2.While
The martensite lath boundaries
after being temperedremain
at 630 ◦ C
intact
(Figure after
2b), thebeing
lathtempered
boundaries at 570 °C exist,
still (Figurebut
2a).its
While after being
integrity tempered
reduces. As at
the630temperature
°C (Figure 2b), the
increased
lath boundaries still exist, but its integrity reduces. As the temperature increased
further, the dislocations in α phase gradually merge and annihilate, then the residual dislocations further, the
dislocations in α phase gradually merge and annihilate, then the residual dislocations
are gradually polygonized in the form of subgrains, resulting in the recovery of lath boundaries are gradually
polygonized in the form of subgrains, resulting in the recovery of lath boundaries (Figure 2c,d) [20–22].
(Figure 2c,d) [20–22]. Moreover, as already reported [22,23], the dislocation density decreases with
Moreover, as already reported [22,23], the dislocation density decreases with increasing tempering
increasing tempering temperature while there still contains a high density of dislocations even after
temperature while there still contains a high density of dislocations even after 720 °C tempering
720 ◦ C tempering
(Figure 2d). (Figure 2d).

Figure 1. SEM microstructures of 42CrMo4-V steel tempered at: (a) 570 °C; (b) 600 °C; (c) 630 °C; (d)
Figure 1. SEM microstructures of 42CrMo4-V steel tempered at: (a) 570 ◦ C; (b) 600 ◦ C; (c) 630 ◦ C;
660 °C; (e) 690 °C; (f) 720 °C.
(d) 660 ◦ C; (e) 690 ◦ C; (f) 720 ◦ C.
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Figure 2. TEM images showing the recovery of martensite lath in 42CrMo4-V steel tempered at:
Figure 2. TEM images showing the recovery of martensite lath in 42CrMo4-V steel tempered at:
(a) 570 °C; (b) 630 °C; (c) 720 °C; (d) 720 °C.
(a) 570 ◦ C; (b) 630 ◦ C; (c) 720 ◦ C; (d) 720 ◦ C.
Figure 1 reflects not only the recovery of martensite laths, but also the evolution of carbides with
increase 1inreflects
Figure tempering
nottemperature. After being
only the recovery oftempered
martensite at 570 °C (Figure
laths, 1a) the
but also and evolution
600 °C (Figure 1b),
of carbides
carbides precipitate preferentially along the martensite lath boundaries
with increase in tempering temperature. After being tempered at 570 C (Figure 1a) and 600 ◦ C because
◦ of low thermal
activation energy. Meanwhile, the carbides are mainly strip-like shape with high length to width. After
(Figure 1b), carbides precipitate preferentially along the martensite lath boundaries because of low
tempering at 630 °C (Figure 1c) and 660 °C (Figure 1d), carbides precipitated within laths increase and
thermal activation energy. Meanwhile, the carbides are mainly strip-like shape with high length
carbides precipitated along laths ◦transform to short rod-like.◦ When the temperature eventually
to width. After tempering at 630 C (Figure 1c) and 660 C (Figure 1d), carbides precipitated
increased to 720 °C (Figure 1f), adjacent interfaces merge and precipitates gather at subgrains.
within laths
Meanwhile, increase and
carbides havecarbides precipitated
been spheroidized andalong
coarsenlaths transform to short rod-like. When the
obviously.
◦
temperature XRDeventually
tests are used to determine
increased to 720 the type of carbide
C (Figure precipitates
1f), adjacent with merge
interfaces different
andtempering
precipitates
gathertemperatures.
at subgrains. The results are shown
Meanwhile, carbides in Figure
have been 3. After being tempered
spheroidized at 570 °C,obviously.
and coarsen there are mainly
V-richtests
XRD M8C7 are carbides
usedand toFe-rich M3C type
determine the carbides.
type of With the increase
carbide in tempering
precipitates temperature,
with different the
tempering
diffraction peak intensity of M 8C 7 is getting lower and lower, which means
temperatures. The results are shown in Figure 3. After being tempered at 570 C, there are mainly that the
◦ relative content
V-richofMM8CC7 type carbide is decreasing. When the tempering temperature is over 690 °C, the M8C7 type
8 7 carbides and Fe-rich M3 C type carbides. With the increase in tempering temperature, the
carbides almost disappear. Thus, the carbide precipitation sequence is M8C7 → M3C.
diffraction peak intensity of M8 C7 is getting lower and lower, which means that the relative content
of M8 C7 type carbide is decreasing. When the tempering temperature is over 690 ◦ C, the M8 C7 type
carbides almost disappear. Thus, the carbide precipitation sequence is M8 C7 → M3 C.
Metals 2018, 8, 232 5 of 12
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Figure 3.
Figure 3. XRD
XRD spectra
spectra of
of carbides
carbides in
in 42CrMo4-V
42CrMo4-V steel
steel tempered
tempered at
at 570–720
570–720 ◦°C
C.

It is noteworthy that the presence of M23C6 carbides is not observed in our experiment, whereas
It is noteworthy that the presence of M23 C6 carbides is not observed in our experiment, whereas
the existence of this type of carbide in other low alloy Cr-Mo steel after tempering is reported in
the existence of this type of carbide in other low alloy Cr-Mo steel after tempering is reported in
published literature [24,25]. The precipitation temperatures of V-rich M8C7 and Cr-rich M23C6 are
published literature [24,25]. The precipitation temperatures of V-rich M8 C7 and Cr-rich M23 C6 are
calculated to explain the difference. According to the relevant chemical equation and thermodynamic
calculated to explain the difference. According to the relevant chemical equation and thermodynamic
data [26–29], a precipitation reaction of Cr23C6 and V8C7 is obtained.
data [26–29], a precipitation reaction of Cr23 C6 and V8 C7 is obtained.
23[Cr] + 6[C] = Cr23C6 (s), ∆𝐺 ∅ = −959,797.18 + 1172.69𝑇 (1)
23[Cr] + 6[C] = Cr23 C6 (s), ∅∆GT∅ = −959, 797.18 + 1172.69T (1)
8[V] + 7[C] = V8C7 (s), ∆𝐺 = −1,430,674.45 + 865.36𝑇 (2)
The equilibrium 8solubility
[V] + 7[Cproduct
] = V8 C7of , ∆G
(s)Cr 23CT
6 and
∅
= −V1,8C 7 obtained
430, 674.45 +from Equations (1) and (2) are
865.36T (2)
givenThe
by the following:
equilibrium solubility product of Cr C and V C obtained from Equations (1) and (2) are
23 6 8 7
given by the following: 115,443.49
In(𝑤[Cr]% · 𝑤[C]% ) = 141.05 −115, 443.49 (3)
23 6
In(w[Cr]% ·w[C]% ) = 141.05 − 𝑇 (3)
T
21,510.02
In 𝑤[V]% · 𝑤[C]% .
= 13.01 −21, 510.02 (4)
In(w[V]% ·w[C]0.875 ) = 13.01 − 𝑇 (4)
%
T
The precipitation temperatures of these carbides can be obtained by inserting the following
The
values precipitation
into Equations temperatures of these
(3) and (4): w[Cr] % =carbides
1.12, w[V]can %be=obtained
0.19, andbyw[C]
inserting the following
% = 0.40. values
The results are
into Equations (3)
shown as following:and (4): w[Cr] % = 1.12, w[V] % = 0.19, and w[C] % = 0.40. The results are shown as
following:
T TM23=C6529 °C ◦ C
= 529 (5)(5)
◦
TTM8 C7 = 1117 °C
= 1117 C (6)(6)
When
When thethe temperature
temperatureisisbelowbelowthe theprecipitation
precipitation temperature,
temperature, thethe carbides
carbides willwill precipitate.
precipitate. In
In this
this study,
study, alltest
all the the temperatures
test temperatures are higher
are higher 529 ◦529
than than C, so°C,
Mso23 CM C6 cannot
cannot
6 23 be precipitated.
be precipitated.
Further observations
observations on the morphologies and compositions of carbides of 42CrMo4-V steel
tempered at atvarious
varioustemperatures
temperatures areare shown
shown in Figure
in Figure 4. Combined
4. Combined with results
with XRD XRD results
and EDXandresults,
EDX
results,
it can beitfound
can bethat
found
afterthat after
being tempered at 570 ◦ Cat(Figure
being tempered 570 °C4a)(Figure
the long 4a) strip-like
the long strip-like carbides
carbides are are
M3 C and
◦ C (Figure 4b), the short
M3C and most of them are between 300 nm and 600 nm. After being tempered at 630 °C (Figure 4b),
most of them are between 300 nm and 600 nm. After being tempered at 630
the shortcarbides
rod-like rod-likearecarbides
M3 C andare theMspherical
3C and the spherical
carbides are Mcarbides
8 C7 . The are M8C
length of7.MThe length
3 C are of M
150–300 3C and
nm are
◦ C (Figure 4c), the
150–300 nm and the
the diameter of M 8 7 diameter of M8C7 are less than 100 nm. When the temperature increased to
C are less than 100 nm. When the temperature increased to 720
720 °C (Figure
irregular 4c), the
spherical irregular
carbides are M spherical
3 C with carbides
a diameter areofM150–200
3C with nm.a diameter of 150–200 nm.
From the above results, it can be found that with increasing tempering temperature, the
spheroidizing process of M3C carbides can be divided into two stages. First, the lengths of M3C
Metals 2018, 8, 232 6 of 12

From the above results, it can be found that with increasing tempering temperature, the
Metals 2018, 8, x FOR PEER REVIEW 6 of 12
spheroidizing process of M3 C carbides can be divided into two stages. First, the lengths of M3 C
carbides diminish
carbides diminish from
from 300–600
300–600 nm
nm to
to 150–200
150–200 nm
nm while
while the
the widths
widths are
are basically
basically unchanged.
unchanged. Second,
Second,
the widths of M3C carbides coarsen but the lengths remain unchanged. The changes in the length and
the widths of M C carbides coarsen but the lengths remain unchanged. The changes in the length and
width of M3C carbides are carried out separately rather than simultaneously.
width of M C carbides are carried out separately rather than simultaneously.

Figure
Figure 4.
4. TEM
TEMandandEDX EDXresults
resultsshowing
showingthe
theevolution
evolutionofof
carbides in in
carbides 42CrMo4-V steel
42CrMo4-V tempered
steel at (a)
tempered at
570570
(a) °C;◦(b) 630630
C; (b) °C; ◦(c)
C; 720 °C. ◦ C.
(c) 720

Furthermore, according to experimental results and theoretical calculations combined with

Furthermore, according to experimental results and theoretical calculations combined with
published literature, it can be concluded that M8C7 carbides precipitate at a higher temperature
published literature, it can be concluded that M8 C7 carbides precipitate at a higher temperature
(about 1390 K), but it has a slow coarsening speed (Figure 4b). While M3C carbides precipitate at a
(about 1390 K), but it has a slow coarsening speed (Figure 4b). While M3 C carbides precipitate at a lower
lower temperature (about 1023 K) [30], but it has a fast coarsening speed (Figure 4b). The reason is
temperature (about 1023 K) [30], but it has a fast coarsening speed (Figure 4b). The reason is mainly
mainly that Fe and Cr have greater diffusion rate than that of V [29]. The driving force of the
that Fe and Cr have greater diffusion rate than that of V [29]. The driving force of the precipitation
precipitation of M8C7 carbides is larger because of its higher precipitation temperature, so the
of M8 C7 carbides is larger because of its higher precipitation temperature, so the requirement of the
requirement of the nucleation sites of M8C7 carbides is lower and M8C7 carbides are more widely
nucleation sites of M8 C7 carbides is lower and M8 C7 carbides are more widely dispersed.
dispersed.
3.2. Impact Energy
3.2. Impact Energy
Figure 5 shows the absorbed energy of 42CrMo4-V steel tempered at different temperatures. The
Figure 5 shows the absorbed energy of 42CrMo4-V steel tempered at different temperatures. The
absorbed energies of 42CrMo4-V steel were found to increase significantly from 21.7 J to 132.3 J with
absorbed energies of 42CrMo4-V steel were found to increase significantly from 21.7 J to 132.3 J with
increasing tempering temperatures from 570 ◦ C to 720 ◦ C. The fracture surfaces of impact specimens are
increasing tempering temperatures from 570 °C to 720 °C. The fracture surfaces of impact specimens
shown in Figure 6. Only the samples with representative result are displayed. The macro fractographs
are shown in Figure 6. Only the samples with representative result are displayed. The macro
are shown in Figure 6a–f. After the 570 ◦ C temper (Figure 6a), the radial region, which is known as
fractographs are shown in Figure 6a–f. After the 570 °C temper (Figure 6a), the radial region, which
the crack unstable propagation region as well as the crack rapid propagation region, takes up most
is known as the crack unstable propagation region as well as the crack rapid propagation region,
of the fracture surface and the shear lip is thin, indicating that the failure mode is a brittle fracture.
takes up most of the fracture surface and the shear lip is thin, indicating that the failure mode is a
The thickness of shear lip increases and the area of radial region reduces with increasing tempering
brittle fracture. The thickness of shear lip increases and the area of radial region reduces with
temperatures from 600 ◦ C (Figure 6b) to 720 ◦ C (Figure 6f), indicating that the mode of fracture evolves
increasing tempering temperatures from 600 °C (Figure 6b) to 720 °C (Figure 6f), indicating that the
from brittle to ductile as the tempering temperature rise [31]. Figure 6g–i is high-magnification images
mode of fracture evolves from brittle to ductile as the tempering temperature rise [31]. Figure 6g–i is
of zone 1, 3 and 5 in Figure 6a–f, respectively. With increasing tempering temperature, the dimple
high-magnification images of zone 1, 3 and 5 in Figure 6a–f, respectively. With increasing tempering
fractures in radial region increase, indicating that the failure mode of radial region transforms from
temperature, the dimple fractures in radial region increase, indicating that the failure mode of radial
cleavage fractures to quasi-cleavage fractures, a failure mode between brittle fracture and ductile
region transforms from cleavage fractures to quasi-cleavage fractures, a failure mode between brittle
fracture. Figure 6j–l is high-magnification images of zone 2, 4 and 6 in Figure 6a–f, respectively. It
fracture and ductile fracture. Figure 6j–l is high-magnification images of zone 2, 4 and 6 in Figure 6a–f,
can be found that dimples in fibrous zones become larger and deeper with increasing tempering
respectively. It can be found that dimples in fibrous zones become larger and deeper with increasing
tempering temperature. A large number of microscopic voids form and grow inside the metal under
the external force. The sample fractures when the voids connect to each other. The void remained in
the fracture surfaces is the dimple. The large size of dimple means that the material has a large plastic
Metals 2018, 8, 232 7 of 12

temperature. A large number of microscopic voids form and grow inside the metal under the external
force. The 8,sample
Metals 2018, x FOR PEER fractures
REVIEWwhen the voids connect to each other. The void remained in the fracture 7 of 12
surfaces is the dimple. The large size of dimple means that the material has a large plastic deformation
deformation
before before the
the fracture, so fracture,
samples so samples
with largewith largehave
dimples dimples have a preferable
a preferable impact toughness
impact toughness [23,32].[23,32].
With
WithMetals
increasing
increasing 2018, tempering
8, x FOR
tempering PEER temperature
REVIEW
temperature from 570from
◦ C 570 °C◦to
to 720 C, 720 °C, the proportion
the proportion of dimple offractures
dimple7 of
fractures
12
increase
increase
and and the dimples
the dimples become
become larger larger
and andresulting
deeper, deeper, resulting in the increase
in the increase of absorbed
of absorbed energy [23].
energy [23].
deformation before the fracture, so samples with large dimples have a preferable impact toughness [23,32].
With increasing tempering temperature from 570 °C to 720 °C, the proportion of dimple fractures
increase and the dimples become larger and deeper, resulting in the increase of absorbed energy [23].

Figure 5.
Figure 5. Absorbed
Absorbed energy
energy at
at −
−30
30 °C
◦ C of
of 42CrMo4-V
42CrMo4-V steel
steel tempered
tempered at
at different
different temperature.
temperature.
Figure 5. Absorbed energy at −30 °C of 42CrMo4-V steel tempered at different temperature.

Figure 6. Cont.
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Figure 6. Macro fractographs of 42CrMo4-V steel tempered at (a) 570 °C; (b) 600 °C; (c) 630 °C; (d) 660 °C;
◦ C; (b) 600 ◦ C; (c) 630 ◦ C;
Figure
Figure 6.6.Macro
Macro fractographs of 42CrMo4-V
fractographs steel steel
of 42CrMo4-V tempered at (a) 570
tempered °C; 570
at (a) (b) 600 °C; (c) 630 °C; (d) 660 °C;
(e) 690 °C; (f) 720 °C; (g–i) are high-magnification images of zone 1, 3 and 5 in (a–f), respectively,
◦ C; (e) 690 ◦ C; (f) 720 ◦ C; (g–i) are high-magnification images of zone 1, 3 and 5 in (a–f),
(e)
(d) 690
660 °C; (f) 720 °C; (g–i) are high-magnification images of zone 1, 3
(j–k) are high-magnification images of zone 2, 4 and 6 in (a–f), respectively.and 5 in (a–f), respectively,
(j–k) are high-magnification
respectively, images of zone
(j–k) are high-magnification 2, 4 and
images 6 in (a–f),
of zone respectively.
2, 4 and 6 in (a–f), respectively.
3.3. Mechanisms
3.3.
3.3. Mechanisms
Mechanisms
It can be seen that the low temperature toughness increases significantly with the increase of
tempering
It
It can
can be be seentemperature.
seen that theAlow
that the major
low factor for thetoughness
temperature
temperature increase is the
toughness softening
increases
increases of matrix. During
significantly
significantly withthe
with thefracture
the increase
increase of of
process,
tempering the
tempering temperature. propagation
temperature. A A majorof a crack
major factor depends
factor forfor the on the
the increase stress
increase is concentration
is the
the softening
softening of at the crack
of matrix. tip.
matrix. During When
During the the
the fracture
fracture
stress concentration is high enough to exceed the yield strength of the metal, plastic deformation
process,
process, thethepropagation
propagationofofa acrack crack depends
depends on on
thethe stress
stress concentration
concentration at theatcrack
the crack tip. When
tip. When the stressthe
occurs and there is a plastic deformation region around the crack tip. Furthermore, the softer the base
stress concentration
concentration is high is high enough
enough to exceed totheexceed
yieldthe yield of
strength strength of the
the metal, metal,
plastic plastic deformation
deformation occurs and
metal, the larger the plastic deformation region. Additionally, large plastic deformation district will
occurs isand
thereresult there deformation
a plastic
in slower
is acrack
plastic deformation
region and
propagation aroundregion
largerthe around
crack tip.
absorbed
theFurthermore,
energy
crack tip. Furthermore,
[23]. the softer thethebase
softer the base
metal, the
metal, theThere
larger the larger
plastic the plastic deformation region. Additionally, large plastic
are mainly two reasons for the softening of the base metal: the decrease of dislocation in
deformation region. Additionally, large plastic deformation deformation
district district
will result will
result
slower in slower
strengthening crack
crack propagation and propagation
solidandsolution
larger and larger absorbed
strengthening.
absorbed energyof[23].
The decrease
energy [23]. dislocation strengthening is due to
There
the decrease
There are
are mainly two
of dislocation
mainly reasons
density.for
two reasons for the
Thethe softening
dislocation
softening of the
density
of the base metal:
of base metal:steel
42CrMo4-V the decrease
decreaseatof
thetempered dislocation
ofdifferent
dislocation
strengthening
temperatures
strengthening and
andwas solid solution
calculated
solid solution fromstrengthening.
XRD spectra (Figure
strengthening. The
The decrease
7) and the
decrease of dislocation
ofresults are shown
dislocation strengthening is
in Figure 8. With
strengthening is due
due toto
the increasing
the decrease
decrease of tempering
of dislocation temperature
dislocation density.
density. The from 570
The dislocation °C to
dislocation density720 °C,
density of the dislocation
of 42CrMo4-V
42CrMo4-V steel density decreased
steel tempered
tempered at from
at different
different
4.08 × 1014was
temperatures
temperatures ·m−2 to
was 0.94 × 1014from
calculated
calculated ·m−2. With
from XRDincreasing
XRD spectra tempering
spectra (Figure
(Figure 7) temperature,
7) and
and the
the resultstheare
results dislocations
are shown
shown in inmove,
Figure
Figure then8.
8. With
With
merge and eventually annihilate, leading ◦to the reduction of dislocation density. Moreover,
increasing tempering temperature from 570 °C to 720 °C,
◦
increasing tempering temperature from 570 C to 720 C, the dislocation density decreased from the dislocation density decreased from
dislocation movement 14can14 relieve
−2 .the local stress concentration. As a result, crack initiation delays.
4.08
4.08 ××10 ·m
101414 ·m−2 −to2 0.94
to 0.94× 10× 10·m−2·. m With increasing
With tempering
increasing temperingtemperature, the dislocations
temperature, move,move,
the dislocations then
Once the crack is initiated, dislocation movement can reduce the stress peak at the crack tip and
merge
then hinderand the
merge eventually
and eventually annihilate,
annihilate,
crack propagation [22].
leading
leadingto the
to the reduction
reduction ofofdislocation
dislocation density.
density. Moreover,
Moreover,
dislocation
dislocation movement
movement can can relieve
relieve the the local
local stress
stress concentration.
concentration. As As aa result,
result, crack
crack initiation
initiation delays.
delays.
Once
Once thethe crack
crackisisinitiated,
initiated,dislocation
dislocation movement
movement cancanreducereduce the stress
the stress peak peak
at theatcrack
the tipcrack
andtip and
hinder
hinder
the crack thepropagation
crack propagation [22]. [22].

Figure 7. XRD spectra of 42CrMo4-V steel tempered at 570–720 °C.

Figure
Figure 7.
7. XRD
XRD spectra
spectra of
of 42CrMo4-V
42CrMo4-V steel
steel tempered
tempered at
at 570–720
570–720 ◦°C.
C.
Metals 2018, 8, 232 9 of 12
Metals 2018,
Metals 2018, 8,
8, xx FOR
FOR PEER
PEER REVIEW
REVIEW 99 of
of 12
12

Figure 8.
Figure
Figure 8. Dislocation
8. Dislocation density
Dislocation density of
density of 42CrMo4-V
of 42CrMo4-Vsteel
42CrMo4-V steeltempered
steel temperedat
tempered at570–720
at 570–720◦°C.
570–720 °C.
C.

Figure 9.
Figure
Figure 9. Percentage
9. Percentage of
Percentage of carbides
of carbides in
carbides in42CrMo4-V
in 42CrMo4-Vsteel
42CrMo4-V steeltempered
steel temperedat
tempered at570–720
at 570–720◦°C.
570–720 °C.
C.

The decrease
The
The decrease of
decrease of solid
of solid solution
solid solution strengthening
solution strengtheningis
strengthening is mainly
is mainly due
mainly due to
due to the
to the precipitation
the precipitation of
precipitation of carbide,
of carbide, which
carbide, which
which
leadstoto
leads
leads tothe
the
the decrease
decrease
decrease of degree
of
of the the degree
the degree of supersaturation
of supersaturation
of supersaturation of the
of
of the matrix the[33].
matrix
matrix [33].
[33].
Figure Figure
Figure
9 shows the99relationship
shows the
shows the
relationship
relationship between
between the
the percentage
percentage of
of carbides
carbides and
and the
the tempering
tempering
between the percentage of carbides and the tempering temperature. It demonstrates that the percentage temperature.
temperature. It
It demonstrates
demonstrates that
that
thecarbides
the
of percentage
percentage of carbides
of
increases carbides
with increases
increases
the increase with the
with
in tempering the temperature.
increase in
increase in tempering
tempering
The temperature.
temperature.
more precipitates meanTheThe more
more
the more
precipitates
precipitates mean
mean the
the more
more interstitial
interstitial atoms,
atoms, especially
especially CC atoms,
atoms,
interstitial atoms, especially C atoms, dissolve in the matrix precipitated from the supersaturationdissolve
dissolve in
in the
the matrix
matrix precipitated
precipitated
from solution,
from
solid the supersaturation
the supersaturation
resulting insolid solid solution, resulting
the solution,
decrease resulting
of the degree in the
in the decrease
ofdecrease of the
of
supersaturation.the degree
degree of supersaturation.
of
In 42CrMo4-Vsupersaturation.
steel, withIn
In
42CrMo4-V
42CrMo4-V
increasing steel, with
steel,
tempering with increasingfrom
increasing
temperature tempering
tempering temperature
570 ◦ Ctemperature
to 720 ◦ C, thefromfrom
matrix 570metal
570 °C to
°C tobecomes
720 °C,
720 °C, softer,
the matrix
the matrix metal
metal
the plastic
becomes
becomes softer,
softer, the
the plastic
plastic deformation
deformation region
region around
around the
the crack
crack
deformation region around the crack tip becomes larger, resulting in a preferable low temperature tip
tip becomes
becomes larger,
larger, resulting
resulting in aa
in
preferable
preferable low
low
impact toughness. temperature
temperature impact
impact toughness.
toughness.
Another factor
Another
Another factor for
factor for the
for the increase
the increase in
increase in low
in low temperature
low temperature impact
temperature impact toughness
impact toughness is
toughness is the
is the evolution
the evolution
evolution of of carbides.
of carbides.
carbides.
The
The evolution
evolution includes
includes three
three aspects:
aspects: morphology,
morphology, distribution
distribution
The evolution includes three aspects: morphology, distribution and size. The morphologies of carbides and
and size.
size. The
The morphologies
morphologies of
of
carbides
carbides
change change
change
from lamellafrom
from lamella
lamella
to short toand
rodto short
short rodto
rod
finally and
and finally as
finally
globosity tothe
to globosity
globosity
tempering as the
as the tempering
tempering
temperature temperature
temperature
increases from
increases
increases
◦ from
from ◦ 570
570 °C
°C to
to 720
720 °C.
°C. Meanwhile,
Meanwhile, the
the distribution
distribution
570 C to 720 C. Meanwhile, the distribution of carbides changes gradually from the continuousof
of carbides
carbides changes
changes gradually
gradually from the
from the
continuous
continuous distribution
distribution along
along the
the martensite
martensite lath
lath to
to the
the dispersive
dispersive distribution.
distribution.
distribution along the martensite lath to the dispersive distribution. The lamellar carbide is a brittle The
The lamellar
lamellar carbide
carbide
is aa brittle
is
phase, brittle phase,
and itphase,
is easyandand it is
it
to produce is easy
easy to produce
to
lager produce
stress lager stress
lager
concentration stresswhich
concentration
concentration
in turn leads which
which in turn
in turn leads
to microcracks leads to
to
[34].
microcracks
microcracks [34].
[34]. Further,
Further, microcracks
microcracks can
can expand
expand rapidly
rapidly along
along
Further, microcracks can expand rapidly along the continuously distributed lamellar carbides [35]. the
the continuously
continuously distributed
distributed
lamellar carbides
lamellar carbides [35].[35]. AsAs aa result,
result, aa poor
poor low
low temperature
temperature impact impact toughness
toughness of of 42CrMo4-V
42CrMo4-V steel steel is
is
obtained after
obtained after tempering
tempering at at 570
570 °C,
°C, only
only about
about 21.721.7 J.J. With
With thethe increase
increase of of tempering
tempering temperature,
temperature,
Metals 2018, 8, 232 10 of 12

As a result,
Metals 2018, 8,ax poor low REVIEW
FOR PEER temperature impact toughness of 42CrMo4-V steel is obtained after tempering 10 of 12
at 570 ◦ C, only about 21.7 J. With the increase of tempering temperature, the stress concentration
the stress concentration
decreases significantly whendecreases significantly
the carbides becomewhen the stick,
short carbides become
leading short
to the stick, leading
significant increaseto the
of
significant
crack formingincrease of crack
energy. forming
Moreover, as energy. Moreover,
the carbide was noaslonger
the carbide was no the
continuous, longer
crackcontinuous,
propagation the
crack propagation
becomes difficult, so becomes
the crackdifficult, so theenergy
propagation crack propagation
also increases. energy
Afteralso
beingincreases.
tempered After being
at 720 ◦ C,

tempered
carbide at 720 °C,dispersed
precipitates carbide precipitates dispersed
in the globosity, so thereinisthe globosity,
a further so there
increase is crack
in the a further increase
forming energyin
the crack
and formingenergy
propagation energyandandthepropagation energyincrease
absorbed energy and the to absorbed energy
about 132.3 J. increase to about 132.3 J.
The grain
The grain structure
structure also
also has
has an
an important
important effect
effect inin the
the low
low temperature
temperature impact
impact toughness
toughness of of
42CrMo4-Vsteel.
42CrMo4-V steel.From
FromFigure
Figure10,10,
thethe percentage
percentage of grain
of grain misorientation
misorientation angle angle
higherhigher
than 15than 15° is
◦ is 46.91%

46.91%tempering
when when tempering
at 720 ◦ C,atwhile,
720 °C,it iswhile, it is only
only 41.28% 41.28%
at 570 at 570 °C, indicating that some lath
◦ C, indicating that some lath boundaries

boundaries
change change
gradually fromgradually
the small from
angle the small to
boundary angle boundary
the large to the large
angle boundary withangle boundary
increasing with
tempering
increasing tempering
temperature. The reason temperature.
for this trendThe reason
is the for thismovement
dislocation trend is the anddislocation
the recovery movement andlath.
of martensite the
recovery of martensite lath. During the fracture process, the crack propagation direction will be
During the fracture process, the crack propagation direction will be changed when it suffers the large
changed
angle when it suffers
boundaries, the in
resulting large
the angle
windingboundaries, resulting in
crack propagation the winding
paths crack propagation
and the larger paths
crack propagation
and the[36,37].
energy larger crack propagation
As a result, energy [36,37].
high temperature As a result,
tempering with high
largertemperature
amount of largetempering with larger
angle boundaries
amount
leads to aofpreferable
large angle boundaries leads to a preferable toughness.
toughness.

Figure 10. EBSD images and misorientations when tempered at: (a) 570 °C; (b) 720 °C.
Figure 10. EBSD images and misorientations when tempered at: (a) 570 ◦ C; (b) 720 ◦ C.

4. Conclusions
The effect of tempering temperature on the low temperature impact toughness of 42CrMo4-V
steel is studied on the basis of microstructures after tempering at 570–720 °C for 3 h. The results are
summarized as follows:
Metals 2018, 8, 232 11 of 12

4. Conclusions
The effect of tempering temperature on the low temperature impact toughness of 42CrMo4-V
steel is studied on the basis of microstructures after tempering at 570–720 ◦ C for 3 h. The results are
summarized as follows:

1. The addition of V to 42CrMo4 steel leads to the appearance of M8 C7 type carbides, and the carbide
precipitation sequence of 42CrMo4-V steel is M8 C7 → M3 C. As the tempering temperature
increases, the spheroidizing process of M3 C carbides can be divided into two stages and it has a
significant effect on the low temperature impact toughness.
2. With the increase of tempering temperature from 570 ◦ C to 720 ◦ C, the low temperature impact
energy of 42CrMo4-V steel increases greatly from 26 J to 132 J. The changes of toughness
are attributed to the evolution of microstructure, including the softening of matrix metal,
the evolution of carbide precipitates and grain structures.

Acknowledgments: This work was financially supported by the National Key Research and Development
Program of China (2016YFB0300401).
Author Contributions: Chen Sun carried out the experiments and analysis of the results. Pai-Xian Fu, Hang-Hang
Liu and Ning-Yu Du prepared and revised the manuscript. Hong-Wei Liu contributed in the interpretation and
discussion of results.
Conflicts of Interest: The authors declare no conflict of interest.

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