Materials & Design 83 (2015) 422–430

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Materials & Design

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Superhardenability behavior of vanadium in 40CrNiMoV steel

C. Chen a, F.C. Zhang a,⇑, Z.N. Yang b, C.L. Zheng a
a
State Key Laboratory of Metastable Materials Science and Technology, Yanshan University, Qinhuangdao 066004, China
b
National Engineering Research Center for Equipment and Technology of Cold Strip Rolling, Yanshan University, Qinhuangdao 066004, China

a r t i c l e i n f o a b s t r a c t

Article history: The effects of vanadium on the hardenability, microstructures and mechanical properties of 40CrNiMoV
Received 19 March 2015 steel were investigated after stabilizing nitrogen with aluminum by using an electron microprobe, a scan-
Revised 16 May 2015 ning electron microscope, a transmission electron microscope, and a hardness tester, etc. The existence
Accepted 6 June 2015
state of vanadium in steel was also analyzed. Results showed that aluminum can effectively stabilize
Available online 19 June 2015
nitrogen by producing aluminum nitride. This phenomenon promoted the segregation of solid solution
vanadium in grain boundaries, delayed the transformation of ferrite and improved the stability of austen-
Keywords:
ite. Thus, vanadium can potentially improve the hardenability of steels. Excellent mechanical properties
Superhardenability
Vanadium
of 40CrNiMoV steel were obtained during slow cooling with the addition of vanadium, and this process
Grain boundary segregation can be used to produce heavy section steel components.
Aluminum nitride Ó 2015 Elsevier Ltd. All rights reserved.

1. Introduction showed that the hardenability multiplying factors of steels con-

Quenched and tempered steels are commonly used in harsh
environments involving the application of severe mechanical loads
because of their good strength and toughness [1]. These properties
are endowed by their tempered sorbite microstrucure, which can
be obtained during quenching and tempering. However, approxi-
mately 100% martensite or lower bainite must be obtained during
quenching to obtain tempered sorbite. The overall mechanical
properties of heavy section steel components depend on their
microstructures at mid-thickness region of the components [1].
Steels must possess sufficiently high hardenability to obtain a con-
siderable amount of martensite or lower bainite when the cooling
rate is extremely slow in heavy section steel components during
quenching. Alloying is a common method of improving hardenabil-
ity; in particular, hardenability increases with increasing alloy con-
tent. However, the application of alloying is limited by its high cost.
Vanadium is a microalloying element commonly used to
increase the strength and toughness rather than the hardenability
of microalloyed steels; this process is realized through the precip-
itation strengthening of fine carbonitride particles that are formed
during cooling or tempering and through the grain boundary pin-
ning effect of nitride [2–5]. Previous studies reported contrasting
results regarding the effect of vanadium on steel hardenability.
Grossman, Lamont and Mangonon [6–10] found that vanadium
can effectively improve the hardenability of steels; their results
⇑ Corresponding author.
E-mail address: zfc@ysu.edu.cn (F.C. Zhang).
taining 0.1% vanadium can reach 1.2–1.6. By contrast, other reports
revealed that vanadium exerts either no or a negative effect on
steel hardenability [11]. Garbarz and Pickering [11,12] hypothe-
sized that austenite grain boundaries can be pinned by undissolved
particles formed by microallying elements, which provide a conve-
nient condition for the segregation of vanadium and other ele-
ments. The segregation hinders the nucleation of ferrite in grain
boundaries, delays transformation in high temperature zone and
eventually improves hardenability of steels. Similar to niobium
and titanium, vanadium has a strong chemical affinity for carbon
and nitrogen; this affinity is primarily responsible for the occur-
rence of precipitation and fine grain strengthening. However, the
potential of vanadium to improve hardenability has received
inconsiderable attention because precipitation strengthening is
the dominant process such that vanadium mostly exists as car-
bonitride particles in steels. Hence, vanadium must be present
in solid solution during austenitising rather than in carbonitride
particles to increase steel hardenability.
Titanium nitride, aluminum nitride, and niobium nitride are
more stable than vanadium nitride at high temperatures [2]. This
result suggests that the chemical affinities of titanium, aluminum,
and niobium for nitrogen are stronger than that of vanadium. Thus,
nitrides co-existing in steels are formed in the following order:
titanium nitride, aluminum nitride, niobium nitride, and vanadium
nitride. Studies on boron steels found that nitrogen can be
stabilized by titanium and aluminum, thereby guaranteeing the
content of boron in solid solution in austenite. However, coarse
TiN formed at high temperatures negatively affects fatigue and

http://dx.doi.org/10.1016/j.matdes.2015.06.050
0264-1275/Ó 2015 Elsevier Ltd. All rights reserved.
 C. Chen et al. / Materials & Design 83 (2015) 422–430
low-temperature impact properties [13,14]. Thus, vanadium in
solid solution state is feasible when aluminum instead of vana-
dium combines with nitrogen to form nitrides. In the present
study, we control vanadium dissolved in austenite to ensure segre-
gation in austenite grain boundaries in consideration of thermody-
namics. Different from previous similar studies, the present work
characterizes segregation.
Vanadium was added in 40CrNiMo steel and aluminum con-
tent was appropriately increased to form 40CrNiMoV steel.
Aluminum nitride was formed during high-temperature forging
or austenitising and then the effect of vanadium was investigated
on hardenability with aluminum. The object of the investigation
was heavy section steel components and cooling rates of 0.7
and 0.3 °C/s were selected after austenitising with subsequent
high-temperature tempering. The mechanical properties and
microstructures of 40CrNiMoV and 40CrNiMo steels were then
compared.
2. Materials and methods
The steels used for the experiment were 40CrNiMoV and
40CrNiMo, whose chemical compositions are listed in Table 1.
40CrNiMoV steel was designed by adding vanadium to 40CrNiMo
steel, stabilizing nitrogen with aluminum, and eventually ensuring
that vanadium is dissolved in austenite.
The steels used in the experiment were prepared through
vacuum induction melting and were forged into
600 mm  110 mm  35 mm plates. Round bar specimens of
£30 mm  105 mm were prepared through electric spark line
cutting and then machined into standard samples for end quench-
ing test. Hardenability was tested in accordance with
GB/T225-2006/ISO642:1999, at austenitising temperatures of
800 °C, 860 °C, 900 °C, 950 °C and 1000 °C and a holding time of
30 min. Hardness values were measured at distances of 1.5, 3, 5,
7, 9, 11, 13, and 15 mm from the quenching end and the following
points had intervals of 5 mm. Five samples were tested at each
temperature. The average hardness values of every point in the
Jominy specimens were selected to indicate hardenability at a
specific temperature. The ideal critical diameters of 40CrNiMoV
and 40CrNiMo steels, as well as the hardenability multiplying fac-
tor and hardenability influencing factor of vanadium, were calcu-
lated from the end quenching test results at 860 °C. The content
of vanadium dissolved in austenite was also determined on the
basis of the ideal stoichiometry of second phase particles and the
solubility formula. The dilatometric curves of the two steels were
tested using a Gleeble3500 thermal simulation testing machine
at an austenitising temperature of 860 °C and a cooling rate of
0.7 °C/s. The electron microprobe JXA-8100 was used to analyze
40CrNiMoV steel cooled at a rate of 0.7 °C/s after austenitising,
including samples whose grain boundaries were etched and not
etched. The austenitising temperature of the test steels was
860 °C and cooling rates of 0.7 and 0.3 °C/s were selected followed
by tempering treatment at 630 °C for 1 h. Tension tests were con-
ducted using a MTS hydraulic servo fatigue testing machine in
accordance with GB/T228.1-2010. Impact tests of ‘‘U’’ notch at
room temperature and ‘‘V’’ notch at 20 °C with specifications of
10 mm  10 mm  55 mm were conducted in accordance with
GB/T229-2007. Three samples were involved in each test.
Table 1
Chemical compositions (wt%) of 40CrNiMoV and 40CrNiMo steels.
Test steels Mo V C Si Mn
40CrNiMoV 0.22 0.089 0.39 0.34 0.69
40CrNiMo 0.20 <0.001 0.43 0.35 0.60
423
Impact fracture was observed under an S-4800 cold
field-emission scanning electron microscope, and the chemical
composition of inclusions was determined through energy disper-
sive spectroscopy (EDS). Color tint-etching [15,16] was performed
to etch samples that were not tempered. Corrosive liquid was pre-
pared by mixing 4% picric acid alcohol solution with a small
amount of hydrochloric acid (1 mL per 100 mL of picric solution)
and 10% sodium metabisulfite solution. The austenite grain bound-
aries of the two steels, which were subjected to austenitising at
860 °C for 20 min, were etched using saturated aqueous picric acid
with a small amount of shampoo. Microstructures were observed
under an Axiover 200MAT optical microscope, and the hardness
of each phase was tested using a FM-ARS 9000 micro-hardness tes-
ter. Fine structures were further observed under a TEM-2010 trans-
mission electron microscope. Thin foils were prepared using Gatan
precision polishing systems in 10% perchloric acid alcohol solution
after being thinned down to a thickness of approximately 30 lm
by using silicon carbide paper.
3. Results
3.1. Hardenability of 40CrNiMoV steel
The hardenability curves of 40CrNiMoV and 40CrNiMo steels at
860 °C are shown in Fig. 1. The hardness at the quenching end of
40CrNiMo steel was 57.5HRC, which is greater than the 55.5HRC
of 40CrNiMoV steel. This result can be attributed to the higher car-
bon content of 40CrNiMo steel than that of 40CrNiMoV steel
[17,18]. However, the hardness of 40CrNiMo steel sharply declined
with increasing distance from the quenched end, and the rate of
change decreased when the end quenching distance exceeded
60 mm because the cooling capability of water was smaller than
that of air. Meanwhile, minimal change in hardness was observed
in 40CrNiMoV steel. In contrast to the 40CrNiMo steel, the
40CrNiMoV steel showed greater hardness difference with increas-
ing end quenching distance. Thus, 40CrNiMoV steel possessed bet-
ter hardenability than 40CrNiMo steel.
The hardenability multiplying factor of vanadium was calcu-
lated from hardenability results at an austenitising temperature
of 860 °C. For steels containing 0.1–0.7% carbon, the relationship
between the hardness of 50% martensite and the carbon content
follows the following formula [17,19]:
HRC50 ¼ 23 þ 50  %C ð1Þ
where HRC50 is the hardness of 50% martensite and %C is the weight
percentage of carbon in steels. The hardness of 50% martensite was
42.5HRC in 40CrNiMoV steel and 44.3HRC in 40CrNiMo steel. End
quenching distances corresponding to 42.5HRC and 44.3HRC were
determined in the hardenability curves at 860 °C, and the relative
distance of 40CrNiMo steel was 36 mm. The hardness of
40CrNiMoV steel at 95 mm from the quenching end was 45.3HRC,
which is greater than 42.5HRC. On the basis of the relationship
between the distance from the quenching end and the ideal critical
diameter (DI) [17], the DI of 40CrNiMo steel was 135 mm and the DIv
of 40CrNiMoV steel was 235 mm at an end quenching distance of
95 mm. The hardenability multiplying factor of vanadium (fv)
[17], can be calculated as follows.
f v ¼ DIv =DI ¼ 235 mm=135 mm ¼ 1:741 ð2Þ
P S Cr Ni Al Nb Ti B N
0.006 0.004 0.89 1.54 0.039 0.005 0.005 0.0003 0.0022
0.001 0.003 0.78 1.51 0.037 0.004 0.006 0.0002 0.0046
424 C. Chen et al. / Materials & Design 83 (2015) 422–430
Fig. 1. Hardenability curves of 40CrNiMoV and 40CrNiMo steels at 860 °C.
However, hardenability was influenced by the content of car-
bon, manganese, and chromium. Hence, the hardenability multi-
plying factor was modified in accordance with the relationship
between the content of carbon and the ideal critical diameter of
carbon steels and the multiplying factors of manganese and chro-
mium. The modification factors CC, CMn, and CCr were calculated
as follows.
C C ¼ DI0:43 =DI0:39 ¼ 5:2 mm=4:9 mm ¼ 1:06
C Mn ¼ f Mn0:60 =f Mn0:69 ¼ 3:10=3:41 ¼ 0:91
C Cr ¼ f Cr0:78 =f Cr0:89 ¼ 2:76=3:00 ¼ 0:92
where DI0.43 and DI0.39 are the ideal critical diameters of carbon
steels with the carbon contents of 0.43% and 0.39%, fMn0.60 and
fMn0.69 are the multiplying factors of manganese with contents of
0.60% and 0.69%, and fCr0.78 and fCr0.89 are the multiplying factors
of chromium with contents of 0.78% and 0.89%, respectively.
Hence, the hardenability multiplying factor of vanadium after mod-
ification can be expressed as follows.
f vv ¼ C C  C Mn  C Cr  f v ¼ 1:06  0:91  0:92  1:741 ¼ 1:545
The effect of element contents on hardenability was considered
in the modified hardenability multiplying factor, which is close to
the true value.
3.2. Microstructures and mechanical properties of 40CrNiMoV steel
Microstructure graphs of 40CrNiMoV and 40CrNiMo steels
cooled at rates of 0.7 and 0.3 °C/s after austenitising but not tem-
pered are presented in Fig. 2. In the figure, the brown zone denotes
martensite M and the white zone dotted with blue particles
denotes upper bainite Bu. The figure shows that large amounts of
upper bainite [20] and small amounts of martensite were obtained
in 40CrNiMoV and 40CrNiMo steels at a low cooling rate of 0.3 °C/s.
However, the amount of martensite was higher in 40CrNiMoV steel
than in 40CrNiMo steel (Fig. 2a and b). When the cooling rate was
increased from 0.3 °C/s to 0.7 °C/s, nearly 100% martensite was
obtained in 40CrNiMoV steel, and the proportion of upper bainite
in 40CrNiMo steel decreased with a small amount of martensite
generated. The microhardness of each phase in the two steels after
different cooling rates is listed in Table 2. The hardness of marten-
site was much higher than that of upper bainite. Moreover, the
hardness of martensite did not considerably change, but the hard-
ness of upper bainite obviously increased with increasing harden-
ability and cooling rate. This result was obtained because 100%
upper bainite cannot be obtained during continuous cooling, and
the percentage of martensite mixed in upper bainite increased at
the condition specified above (Fig. 2c). Thus, the hardness of upper
bainite increased at the macro level. Transmission microstructures
at a cooling rate of 0.7 °C/s are presented in Fig. 3. Typical marten-
site lathes are shown in Fig. 3a and c, and a small amount of
retained austenite was found between the lathes.
Microstructures shown in Fig. 3b and d display the presence of
upper bainite and are the same as those described in other studies
[20,21]. Upper bainite, which is composed of bainite ferrite and
island-like cementite particles distributed in parallel along fer-
rite lath boundaries, was observed in the two steels during contin-
uous cooling at a slow rate. Moreover, aluminum nitride
precipitation was detected in 40CrNiMoV steel with its energy
spectrum analysis shown in Fig. 3e and f and no evidence of vana-
dium nitride precipitations could be found. From the view of the
ability of obtaining martensite at the same cooling condition, hard-
enability of 40CrNiMoV steel, compared to that of 40CrNiMo steel,
was increased much with addition of vanadium.
Microstructures tempered at 630 °C for 1 h after austenitising at
860 °C with a cooling rate of 0.7 °C/s are showed in Fig. 4. Uniform
and fine-tempered sorbite was transformed from martensite after
high-temperature tempering in 40CrNiMoV steel. Favorable
strength and toughness can be obtained for this type of structure.
Meanwhile, a small amount of fine-tempered sorbite was observed
at primary martensite zones in 40CrNiMo steel (Fig. 4b). However,
island-like carbides in upper bainite became coarser and unevenly
ð3Þ distributed.
The mechanical properties of 40CrNiMoV and 40CrNiMo steels
ð4Þ after heat treatment are presented in Table 3. The strength of
40CrNiMoV steel reached the highest level of 1222 MPa after cool-
ð5Þ ing at a rate of 0.7 °C/s and tempered at 630 °C for 1 h. The impact
energy of ‘‘V’’ notch at 20 °C was 43J, which was also the maxi-
mum. Under the same heat treatment conditions, the tensile
strength of 40CrNiMo steel was only 884 MPa, which is lower than
that of 40CrNiMoV steel. In addition, the impact energy of ‘‘V’’
notch at 20 °C was 40 J, which is 3J lower than that of
40CrNiMoV steel. The coarse carbides in 40CrNiMo steel weakened
the effect of dispersion strengthening and eventually caused the
low strength. Moreover, the inhibition of crack propagation dimin-
ð6Þ ished, and the coarse carbides negatively influenced impact prop-
erties. The strength and toughness of the two steels decreased to
a particular degree after cooling at a rate of 0.3 °C/s and tempering
at 630 °C. Considering the proportion of martensite and bainite in
Fig. 3, we speculated that the presence of martensite in steels is
the key factor that determines strength and toughness. Moreover,
toughness did not increase solely because of the decrease in
strength. Comparing the properties of the two steels after the same
heat treatment, we proved that the excellent hardenability of
40CrNiMoV steel was crucial to achieve favorable strength and
toughness.
The impact fracture morphology of ‘‘V’’ notch at 20 °C after
cooling at a rate of 0.7 °C/s and tempering at 630 °C and the EDS
analysis of precipitates observed in 40CrNiMoV steel are shown in
Fig. 5. Minimal difference in impact energy but significant difference
in fracture morphology was observed between 40CrNiMoV and
40CrNiMo steels. The fractures of 40CrNiMo steel were caused by
cleavage surfaces with large sizes and some small and shallow dim-
ples, indicating a quasi-cleavage fracture. Meanwhile, dimples of
different sizes and small cleavage surfaces were observed in
40CrNiMoV steel. This difference is caused by the tempered
structures of the two steels. These results imply that the
toughness-brittleness transformation temperature of 40CrNiMoV
steel was lower than that of 40CrNiMo steel. The EDS results of
the precipitates in Fig. 5a are presented in Fig. 5c. The weight per-
centages of aluminum and nitrogen were 58.22% and 33.65%, which
are very close to the ideal stoichiometry of 1.93 in aluminum nitride.
 C. Chen et al. / Materials & Design 83 (2015) 422–430 425

Fig. 2. Microstructures of 40CrNiMoV and 40CrNiMo steels before tempering. (a) 40CrNiMoV steel, 0.3 °C/s; (b) 40CrNiMo steel, 0.3 °C/s; (c) 40CrNiMoV steel, 0.7 °C/s; (d)
40CrNiMo steel, 0.7 °C/s.

Therefore, aluminum nitride precipitated at high temperatures was

Table 2 included in 40CrNiMoV steel with the fact shown in Fig. 3e and f.
Hardness (HV) of each phase in 40CrNiMoV and 40CrNiMo steels. This phenomenon proves the combination of aluminum and nitro-
Test steels The cooling rate of 0.7 °C/s The cooling rate of 0.3 °C/s
gen, and the stability effect of aluminum on nitrogen.

Martensite, Upper bainite, Martensite, Upper

M Bu M bainite, Bu 4. Discussion
40CrNiMoV 651 ± 32 495 ± 33 648 ± 47 382 ± 66
40CrNiMo 671 ± 35 365 ± 46 664 ± 50 324 ± 38 Previous studies revealed that microalloying improves the
hardenability of steels through the segregation of microalloys in
solid solution state to austenite grain boundaries during austenitis-
ing and cooling. This process reduces the grain boundary energy,

Fig. 3. Transmission microstructures of 40CrNiMoV steel (a, b,) and 40CrNiMo steel (c, d) at a cooling rate of 0.7 °C/s before tempering and aluminum nitride precipitation
with its energy spectrum analysis (e, f) detected in 40CrNiMoV steel.
426 C. Chen et al. / Materials & Design 83 (2015) 422–430

Fig. 4. Tempering microstructures of 40CrNiMoV steel (a) and 40CrNiMo steel (b) at 630 °C for 1 h after cooling at a rate of 0.7 °C/s.

Table 3
Mechanical properties of 40CrNiMoV and 40CrNiMo steels.

Test steels Heat treatment Tensile strength (MPa) Yield strength (MPa) Elongation (%) Reduction of area (%) Impact energy of ‘‘V’’
notch at 20 °C (J)
40CrNiMoV 0.7 °C/s + 630 °C tempering 1222 ± 7 1128 ± 2 13.6 ± 0.8 54.0 ± 1.6 43 ± 5
0.3 °C/s + 630 °C tempering 1130 ± 8 983 ± 6 13.2 ± 0.6 53.6 ± 0.9 28 ± 3
40CrNiMo 0.7 °C/s + 630 °C tempering 884 ± 15 697 ± 8 15.9 ± 0.4 62.8 ± 0.4 40 ± 6
0.3 °C/s + 630 °C tempering 833 ± 8 645 ± 7 15.3 ± 0.7 62.1 ± 0.9 30 ± 3

Fig. 5. Impact fractures of ‘‘V’’ notch at 20 °C and the EDS analysis of precipitates in 40CrNiMoV steel. (a) Fracture of 40CrNiMoV steel; (b) fracture of 40CrNiMo steel; (c)
EDS analysis of the precipitate in (a).

improves austenite stability, delays ferrite transformation and
eventually improves steels hardenability. However, studies have
rarely reported on mechanisms to increase solid solubility in steels,
particularly vanadium steels, and aluminum usually functions as a
deoxidizer in steels. Pan et al. [13] revealed that a particular
amount of aluminum can effectively stabilize nitrogen in steels,
thereby preventing the combination of boron and nitrogen. Boron
would then be dissolved in austenite, and the hardenability of
boron steels would increase. Similarly, the chemical affinity of alu-
minum for nitrogen is stronger than that of vanadium. The combi-
nation of vanadium and nitrogen is blocked when aluminum is
incorporated in vanadium-alloyed steels to keep vanadium dis-
solved in austenite. Garbarz and Pickering [12] analyzed the effect
of vanadium content on steel hardenability. They found that steels
with 0.34% vanadium acquire high hardenability, whereas those
with 0% vanadium exhibit poor hardenability. In the present study,
the vanadium contents in the two steels were 0.089% and 0%. The
hardenability of 40CrNiMoV steel with 0.089% vanadium was
much higher than that of 40CrNiMo steel with 0% vanadium.
Comparison of the previous and current results indicates that no
nitrogen stabilizer elements exist in the test steels of Garbarz
and Pickering. The vanadium in their test steels mostly combined
with carbon and nitrogen to form carbonitride, and the hardenabil-
ity even worsened during the following treatment. However, add-
ing 0.34% vanadium in the steel was sufficient to simultaneously
form carbonitride and dissolve in austenite to improve
hardenability. In the present study, an appropriate amount of alu-
minum was added to the steels to form aluminum nitride. As a
result, nitrogen was stabilized by aluminum, and sufficient vana-
dium remained dissolved in austenite. Thus, the hardenability of
40CrNiMoV steel significantly increased. The precipitation
detected in Fig. 5a and c indicates that aluminum and nitrogen
combined.
The content of vanadium dissolved in austenite during austeni-
tising decides the level of hardenability. The content of vanadium
dissolved in austenite at 860 °C was calculated using the formulas
of solid solubility and the ideal stoichiometry of carbon, nitrogen,
and microalloys in carbide and nitride. Titanium and niobium have
a stronger chemical affinity for nitrogen than for carbon. When
they exist in steels at the same time, titanium and niobium will
combine with nitrogen first. The ideal stoichiometries of microal-
loys and nitrogen in titanium nitride, aluminum nitride, niobium
nitride, and vanadium nitride are 3.42, 1.93, 6.63, and 4.24, respec-
tively [22]. The contents of nitrogen stabilized by titanium, alu-
minum, and niobium are 0.0015%, 0.0202%, and 0.0007%,
respectively. The total content of 0.0224% of stabilized nitrogen
was much higher than the content of 0.0022% in 40CrNiMoV steel.
Therefore, vanadium would not combine with nitrogen to form
vanadium nitride. The formula of solid solubility is shown as
follows:
1 gð½V  ½CÞc ¼ 6:72  9500=T ½22; ½23 ð7Þ
 C. Chen et al. / Materials & Design 83 (2015) 422–430 427

where [] is the weight percentage of the element in solid solution
and T is the absolute temperature. Hence, the contents of vanadium
and carbon dissolved in austenite at 860 °C can be expressed as
follows:
½Vc  ½Cc ¼ 0:02163617
Moreover, the ratio of vanadium/carbon in vanadium carbide
should maintain the following ideal stoichiometry:
Vvc=Cvc ¼ 4:24
Hence,
ð0:089  ½Vc Þ=ð0:39  ½Cc Þ ¼ 4:24
The solution can be obtained using Expressions (8) and (10) to
formulate a simultaneous equation as follows:
½Vc ¼ 0:0566; ½Cc ¼ 0:3823
Therefore, the weight percentage of vanadium dissolved in
austenite or effective vanadium in 40CrNiMoV steel at 860 °C
was 0.0566%, which accounts for 63.6% of the total weight percent-
age. The hardenability and property results of the test steels
revealed that the hardenability of 40CrNiMoV steel was improved
by the dissolved vanadium. Moreover, enough aluminum must be
present to ensure complete stabilization of nitrogen. As is known,
acid-soluble aluminum combines with nitrogen. Thus, the ratio
of acid-soluble aluminum to nitrogen should be greater than or
equal to 3–1 on the basis of the ideal stoichiometry of aluminum
and nitrogen in aluminum nitride and the consumption of alu-
minum by other alloys.
In general, the effect of alloys on hardenability is expressed as
the relationship between the total content and the hardenability
multiplying factor [1,3,6]. But for some alloys, it is not all of them
taking part in improving hardenability and those existing in
compound may even have a negative effect [11]. Moreover, the
hardenability multiplying factor correlates with alloy content.
Nevertheless, this factor cannot completely reflect the effect of
alloys. In the present study, effective vanadium and the harden-
ability influencing factor were chosen to express the extent of
influence on hardenability. According to the relationship about cal-
culating hardenability multiplying factors,
f v ¼ 1 þ 1:73  %V ½18
where 1.73 is the hardenability influencing factor and %V is the
weight percentage of vanadium. If 1.73 is replaced by x, then
f v ¼ 1 þ x  %V
The black line at the bottom of the diagram represents the relation-
ship under normal conditions and the slope is 1.73. The slope or
the hardenability influencing factor of the blue dotted line across
the point ‘‘.’’ obtained by Garbarz and Pickering [12] was 5.00.
The hardenability multiplying factor of them was 2.00 with the
ð8Þ
addition of 0.2% vanadium when the austenitising temperature
was 1050 °C and vanadium was completely dissolved in austenite.
The point ‘‘d’’ represents the relationship between an effective
vanadium content of 0.0566% and a hardenability multiplying fac-
ð9Þ tor of 1.545. The base on the point ‘‘d,’’ which is represented by a
red dotted line, was obtained from our investigation with a slope of
9.64. As shown in Fig. 6, the red dotted line exerted the greatest
ð10Þ effect on hardenability. In addition, the hardenability influencing
factor of 9.64 of vanadium was significantly higher than the theo-
retical value 1.73, indicating a superhardenability effect. Compared
with other methods to obtain superhardenability [24] such as
super-heating treatment and simultaneous addition of niobium,
titanium, and vanadium, the method of the current study had
greater application values because only the contents of aluminum
and vanadium need to be adjusted.
Garbarz and Pickering [12], and Adrain [25] obtained unsatis-
factory results when they investigated the influences and mecha-
nisms of alloys to improve steel hardenability. In the present
study, electron microprobe X-ray microanalysis was used to ana-
lyze untempered samples (Fig. 7) after austenitising at 860 °C
and cooling at a rate of 0.7 °C/s. The microstructures of the scan-
ning zone are presented in Fig. 7a and c. The grain boundaries in
40CrNiMoV steel and martensite that was slightly etched can be
observed in Fig. 7a and c. The diagram of the relative concentration
of vanadium and the scanning distance is shown in Fig. 7b and d.
The blue triangles in Fig. 7a and b indicate the corresponding posi-
tion and the relative content of vanadium. As is shown in
Fig. 7a and b, the concentration of vanadium was much higher in
the grain boundaries than in the grains, indicating the segregation
of vanadium. Dilution areas of vanadium appeared in the range of
1–2 lm around the grain boundaries; this phenomenon is consis-
tent with the general laws of thermodynamics. What is more,
higher peaks of vanadium in Fig. 7d than in Fig. 7b were detected
in samples whose grain boundaries were not etched and the dis-
tances between the peaks were with equal to the grain sizes. The
different peak height of vanadium was related to the corrosion of
ð11Þ grain boundaries. Fig. 7 shows the segregation of vanadium dis-
solved in austenite. This process is crucial to increase the harden-
ability of steels containing vanadium. To further study the effect of
grain boundary segregation on steel hardenability, the
ð12Þ

fvv obtained in Formula (6) and the effective content of vanadium in

40CrNiMoV steel were inputted into Formula (12) and the following
result was obtained:

x ¼ 9:64
The calculation results of the hardenability curves of
40CrNiMoV and 40CrNiMo steels showed that the hardenability
multiplying factor was 1.545 with an effective vanadium content
of 0.0566% and that the hardenability influencing factor was 9.64.
It is 5.6 times higher than the theoretical value of 1.73, indicating
the superhardenability effect of vanadium. In the multiplication
formula for calculating ideal critical diameters, the hardenability
multiplying factor of vanadium is usually expressed as
fv = 1 + 1.73%V, where 1.73 is the hardenability influencing factor.
If 1.73 is replaced with x, the value of x would be obtained by
inputting the hardenability multiplying factor and the effective
Fig. 6. Relationship between the vanadium content and the hardenability multi-
content of vanadium into the formula above. In the diagram of plying factor: x1 represents the hardenability influencing factor under normal
relationship between the weight percentage of vanadium and the conditions, x2 represents the result obtained by Garbarz and Pickering, and x3
hardenability multiplying factor, x is the slope of the line (Fig. 6). represents the result obtained in our research.
428 C. Chen et al. / Materials & Design 83 (2015) 422–430
Fig. 7. Electron probe results of 40CrNiMoV steel with grain boundaries etched (a, b) and not etched (c, d).
hardenabilities and grain sizes of 40CrNiMoV and 40CrNiMo steels
at different temperatures of 800 °C, 860 °C, 900 °C, 950 °C, and
1000 °C were analyzed for comparison. The hardenability was indi-
cated by the average hardness value of the points in the Jominy
specimens. In Fig. 8, the hardenabilities of the two steels increased
with increasing austenitising temperature. Moreover, grain size did
not differ much between the two steels but the difference in hard-
enability decreased, although the hardenability of 40CrNiMoV
steel was greater than that of 40CrNiMo steel at the same temper-
ature. A previous study investigated the effect of austenite grain
Fig. 8. Relationship between hardenability, grain size and austenitising tempera-
tures of 40CrNiMoV and 40CrNiMo steels.
boundary mobility on hardenability [12] and found that the grain
boundary mobility accelerates and the grain boundary segregation
of vanadium weakens as the austenitising temperature increases.
Thus, the lower differences in hardenability and similar grain sizes
at higher temperatures between 40CrNiMoV and 40CrNiMo steels
proved the truth of the grain boundary segregation of vanadium.
The significant effect of the combination of vanadium and alu-
minum was confirmed by the hardenability influencing factor of
vanadium and the excellent mechanical properties of 40CrNiMoV
steel after being cooled at a slow rate. However, the hardenability
results were obtained from the hardness values, and the excellent
mechanical properties might be related to the precipitation of
vanadium. Hence, the grain size and microstructures at a slow
cooling rate must be observed to completely verify whether or
not the increase in strength and toughness is caused by harden-
ability enhancement instead of fine grain strengthening and pre-
cipitation strengthening. Fig. 9 shows the austenite grain
boundaries of 40CrNiMoV and 40CrNiMo steels after austenitising
at 860 °C for 20 min. The average grain size of 40CrNiMoV steel
was 17.25 lm and that of 40CrNiMo steel was 17.16 lm. These
values were obtained from the statistics of grain sizes of 15 fields
of view. The grades of grain size of the two steels were both 8.5,
indicating that the grain of 40CrNiMoV steel was not refined with
the addition of vanadium and that high strength and toughness
were not attributable to the fine grain strengthening effect. As
shown in Fig. 2, the volume fraction of martensite was significantly
higher in 40CrNiMoV steel than in 40CrNiMo steel. In addition, no
differences in fine precipitations were observed between the two
steels in TEM analysis and no vanadium nitride particles were
 C. Chen et al. / Materials & Design 83 (2015) 422–430
Fig. 9. Austenite grains of 40CrNiMoV steel (a) and 40CrNiMo steel (b) at 860 °C.
found. These results demonstrate that there is no carbonitride of
vanadium which can refine grain size.
The low austenite transition temperature also indicates
improved hardenability. Dilatometric curves tested at a cooling
rate of 0.7 °C/s are shown in Fig. 10. The initial martensite transfor-
mation temperature of 40CrNiMoV steel was 472 °C, and no obvi-
ous initial bainite transformation temperature was observed.
Vanadium delayed austenite transition at high temperatures. In
other words, hardenability was significantly improved. A second
transformation was observed in 40CrNiMo steel at 458 °C during
cooling. This result can be attributed to the incomplete transforma-
tion of austenite into upper bainite at 677 °C and the presence of a
small amount of carbon-rich austenite. The retained austenite was
then transformed into martensite at a low temperature during
cooling [22]. In conclusion, the superhardenability and excellent
mechanical properties can be ascribed to the effect of vanadium
on hardenability instead of fine grain strengthening and precipita-
tion strengthening.
Previous studies obtained contradicting results on the mecha-
nism underlying the segregation of microalloys to austenite to
improve steel hardenability. The present results elucidated that
vanadium improved steel hardenability through the following
mechanism. In the temperature range at which the proeutectoid
ferrite formed, the diffusion velocity of carbon into austenite was
the decisive factor that controlled the nucleation and growth of
ferrite. The segregation of vanadium in the austenite grain bound-
aries led to the occupation of favorable interstitial sites. This phe-
nomenon hindered the interstitial diffusion of carbon and
eventually reduced the nucleation and growth rate. Moreover,
the vanadium adsorbed in the grain boundaries filled defect sites,
which reduced the grain boundary energy and nucleation driving
force of ferrite. Thus, a new nucleation was difficult to form. The
Fig. 10. Transition temperatures of 40CrNiMoV and 40CrNiMo steels during slow
cooling treatment.
429
two reasons above increased the stability of austenite and
improved the hardenability of steels.
5. Conclusions
1. Nitrogen in steels can be effectively stabilized by aluminum to
form a compound. The ratio of acid-soluble aluminum to
nitrogen should be greater than or equal to 3–1 to ensure the
formation of aluminum nitride and prevent the formation of
vanadium nitride. Thus, a large amount of vanadium could be
dissolved in austenite. Based upon no vanadium nitride formed
in the steel, the content of vanadium dissolved in austenite at
860 °C was 0.0566%, which accounted for 63.6% of the total
amount.
2. The hardenability multiplying factor reached 1.545 with an
effective vanadium content of 0.0566%. The hardenability
influencing factor was 9.64, which is 5.6 times higher than
the normal value. This effect is called superhardenability, which
is crucial in producing heavy section steel components.
3. Vanadium that segregated in austenite grain boundaries and
occupied favorable interstitial sites hindered the diffusion of
carbon and reduced the grain boundary energy. Moreover, they
delayed the transformation of ferrite, increased the stability of
austenite and eventually improved the hardenability of steels.
4. Excellent mechanical properties of 40CrNiMoV steel can be
attributed to high hardenability. The tensile strength was
1222 MPa and the yield strength was 1128 MPa after austenitis-
ing at 860 °C, cooling at 0.7 °C/s, and tempering at 630 °C for
1 h. The impact energy of ‘‘V’’ notch at 20 °C was 43 J, indicat-
ing that the properties of 40CrNiMoV steel were superior to
those of 40CrNiMo steel.
Acknowledgement
This work was supported by the National High Technology
Research and Development Program of China (863 Program) (No.
2012AA03A504).
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