metals

Article
Microstructure and Strengthening-Toughening
Mechanism of Nitrogen-Alloyed 4Cr5Mo2V
Hot-Working Die Steel
Jinbo Gu 1 , Jingyuan Li 1, * and Yulai Chen 2
1 School of Materials Science and Engineering, University of Science & Technology, Beijing 100083, China;
gujinboustb@163.com
2 Engineering Research Institute, University of Science & Technology Beijing, Beijing 100083, China;
yulaic@ustb.edu.cn
* Correspondence: lijy@ustb.edu.cn; Tel.: +86-010-8237-6939

Received: 27 June 2017; Accepted: 10 August 2017; Published: 14 August 2017

Abstract: The microstructure and strengthening-toughening mechanism of a modified 4Cr5Mo2V

hot-working die steel with nitrogen (0.08% N) were investigated using hardness and toughness
measurements, optical microscopy, scanning electron microscopy, X-ray diffraction experiments,
transmission electron microscopy, and dilatometry. The results showed that the nitrogen addition
could increase the hardness and temperability of 4Cr5Mo2V steel without toughness loss with
a suitable heat treatment procedure. The fair match of high strength and toughness of the
nitrogen-alloyed 4Cr5Mo2V steel is associated with the refinement of the prior austenite grain,
the solution hardening of nitrogen atoms, and the increase of retained austenite. Before quenching,
nitrogen tends to precipitate in the form of a large amount of undissolved finer V(C, N), imposing a
stronger effect on restricting the growth of prior austenitic grains and increasing the grain refining
efficiency of VC by 6.8 times according to an estimate. During the quenching process, the nitrogen
decreases the MS of the martensitic transformation, increasing retained austenite, which is a benefit
for toughness. During the tempering process, some of the N atoms in M(C, N) were dissolved in the
matrix, causing crystal lattice distortions, thus boosting the solution reinforcing effect. Meanwhile, the
solid-dissolved nitrogen inhibits the diffusion of carbon, decreasing the growth rate of the carbides
and increasing tempering resistance.

Keywords: strengthening-toughening; nitrogen-alloyed; hot-working die steel; precipitates

1. Introduction
Die steel 4Cr5Mo2V (Uddeholm designation DIEVAR) is a low silicon and high molybdenum
hot-work tool steel developed from H13 die steel specifically for the sake of better heat checking
resistance and gross cracking resistance [1]. Due to excellent hot strength and toughness, it is
increasingly employed in forging, hot-extrusion, and die-casting. In the case of the ever-growing
requirements of industrial applications, better-quality tool steel is continually needed to increase the
service life of tool steel. Many studies have illustrated the great interest in improving the performance
of die steel [2–4]. Improvement of properties of tool steels can be achieved through improving the
hardness and toughness by adjusting the constituents or optimization of the production technology
such as a deep cryogenic treatment [5,6]. Several new trends in optimizing chemical composition such
as Nb-microalloying or Rare Earth addition have been developed to improve the performance [7–9].
It has been acknowledged that nitrogen addition can strengthen Fe-based alloys and improve
the properties of the steel [10,11]. With the implementation of high-pressure melting technology and
the higher nitrogen content in steel, the effect of nitrogen on the microstructure and the properties of

Metals 2017, 7, 310; doi:10.3390/met7080310 www.mdpi.com/journal/metals

Metals 2017, 7, 310 2 of 14

steel have been investigated thoroughly, especially in austenitic stainless steel [12]. Simmons et al.,
suggested that nitrogen plays a more effective role in solution strengthening and grain refinement
than Metals
carbon 2017, 7, 310
[13]. Werner et al. reported that nitrogen can obviously increase the strength of2austenitic of 14

stainless steels without a significant loss of ductility or impact toughness of the steel [14]. Behjati et al.
steel have been investigated thoroughly, especially in austenitic stainless steel [12]. Simmons et al.,
demonstrated
suggested that the nitrogen
that nitrogen playsexisting
a more as a solution
effective element
role in is strengthening
solution much more effective
and grain than that existing
refinement
in the
thanform of carbonitrides,
carbon [13]. Werner et al.since carbonitrides
reported that nitrogenhave a harmful
can obviously effectthe
increase onstrength
impactoftoughness
austenitic [15].
However,
stainlessthere have
steels been few
without reports on
a significant lossnitrogen-alloyed die steel.
of ductility or impact In theofpresent
toughness the steelstudy, a new et
[14]. Behjati type of
al. demonstrated that the nitrogen existing as a solution element is much more
nitrogen-alloyed H13 hot-work die steel was investigated. Nitrogen alloying improved the hardness of effective than that
existing
H13 die steelinwith
the form of carbonitrides,
no reduction since carbonitrides
in toughness [16]. However, have a harmful
the effect on impact toughness
strengthening-toughening mechanism
needs[15]. However,
further there haveIn
clarification. been few reports
addition, on nitrogen-alloyed
whether the improvement die steel.
canInbethe presentto
applied study, a new die
4Cr5Mo2V
type of nitrogen-alloyed H13 hot-work die steel was investigated. Nitrogen alloying improved the
steel with a higher amount of nitrogen needs further confirmation.
hardness of H13 die steel with no reduction in toughness [16]. However, the strengthening-
Hence, the aim of this work was to investigate the effect of nitrogen on the microstructure
toughening mechanism needs further clarification. In addition, whether the improvement can be
of 4Cr5Mo2V steel during the heat treatment process. Meanwhile, the strengthening-toughening
applied to 4Cr5Mo2V die steel with a higher amount of nitrogen needs further confirmation.
mechanism of nitrogen-alloyed
Hence, the aim of this work 4Cr5Mo2V hot-working
was to investigate die steel
the effect was further
of nitrogen clarified.
on the microstructure of
4Cr5Mo2V steel during the heat treatment process. Meanwhile, the strengthening-toughening
2. Materials
mechanismandofMethods
nitrogen-alloyed 4Cr5Mo2V hot-working die steel was further clarified.
Two 25 kg ingots of 4Cr5Mo2V steel with the composition listed in Table 1 were prepared using
2. Materials and Methods
a vacuum induction furnace (Jinzhou Boda Co., Ltd., Jinzhou, China). The nitrogen-alloyed steel
Twounder
was melted 25 kg ingots of 4Cr5Mo2V
the protection of steel with the atmosphere
a nitrogen composition listed
of 0.6in MPa
Table and
1 were preparedwas
nitrogen using
added
a vacuum induction furnace (Jinzhou Boda Co., Ltd., Jinzhou, China). The nitrogen-alloyed
during the smelting process in the form of a nitrogen-containing ferrochromium alloy. The ingot wassteel was
melted under
homogenized the protection
at 1250 ◦ C for 3 of
h, amulti-directional
nitrogen atmosphere of 0.6 MPa
hot-forged atand nitrogen wasrange
a temperature added of
during the ◦ C,
850–1150
smelting process in the form of a nitrogen-containing ferrochromium alloy. The ingot was
and then air-cooled to ambient temperature.
homogenized at 1250 °C for 3 h, multi-directional hot-forged at a temperature range of 850–1150 °C,
and then air-cooled to ambient temperature.
Table 1. Chemical compositions of tested steel (wt %).

Table 1. Chemical compositions of tested steel (wt %).

Element C Si Mn Cr Mo V N1
Element
Nitrogen steel 0.33 C 0.5 Si 0.42 Mn Cr
5.3 Mo2.4 V 0.68 N0.08
1
Nitrogen-free steel 0.33
Nitrogen steel 0.33 0.5 0.5 0.400.42 5.4
5.3 2.42.4 0.680.63 0.08-
1 Nitrogen content was measured by thermal the conductometric method after fusion in a current of argon gas. The
Nitrogen-free steel 0.33 0.5 0.40 5.4 2.4 0.63 -
other metallic elements were measured by chemical titration.
1 Nitrogen content was measured by thermal the conductometric method after fusion in a current of

argon gas. The other metallic elements were measured by chemical titration.
Specimens, for spheroidizing annealing (SA), quenching, and the tempering process, measuring
15 mm3 were
15 × 15 ×Specimens, taken from the
for spheroidizing hot forged
annealing (SA),samples. During
quenching, SA,
and the the nitrogen-alloyed
tempering 4Cr5Mo2V
process, measuring
15 × 15 × 15 mm 3 were taken ◦from the hot forged samples. During◦ SA, the ◦ −
nitrogen-alloyed 1 4Cr5Mo2V
samples were heated to 850 C and cooled to below 650 C at a rate of 10 C·h in the furnace,
samples itwere
whereupon washeated to 850out
then taken °C of
andthecooled to below
furnace 650 °C to
and cooled at ambient
a rate of temperature.
10 °C·h−1 in theSubsequently,
furnace,
whereupon it was then taken out of the furnace and cooled to ambient temperature. Subsequently,
during the quenching process, the samples were reheated to and kept at 1000 ◦ C, 1030 ◦ C for 0.5 h,
during the quenching process, the samples were reheated to and kept at 1000 °C, 1030 °C for 0.5 h,
respectively. Thereafter, the samples were oil-quenched to ambient temperature. Finally, the quenched
respectively. Thereafter, the samples were oil-quenched to ambient temperature. Finally, the
samples were tempered at 580 ◦ C, 600 ◦ C, and 650 ◦ C for 2, 4, 6 h, respectively. The heat-treating
quenched samples were tempered at 580 °C, 600 °C, and 650 °C for 2, 4, 6 h, respectively. The heat-
process is asprocess
treating shownisinasFigure
shown1.in Figure 1.

Figure 1. Heat-treatment regime of samples.

Figure 1. Heat-treatment regime of samples.
Metals 2017, 7, 310 3 of 14

Samples with a hardness of more than 48 HRC, which were higher than the hardness of ordinary
4Cr5Mo2V die steel, were selected to subsequently test for impact toughness to obtain an optimum
heat treatment. The specimens for impact toughness test were 11 × 11 × 60 mm3 square bars cut from
forgings. Then, the nitrogen-alloyed steel and nitrogen-free steel were subjected to the optimum heat
treatment with different tempering times ranging from 0 h to 8 h to compare the tempering stability.
The HRC hardness of samples was measured using a TH320 Rockwell Hardness Tester (Beijing
Time Group Co., Ltd., Beijing, China) at five points on each sample and the mean value was calculated
(ASTM E18-15). The impact toughness of the heat-treated sample was tested in a JB-30B impact
testing machine (Jinan Hensgrand instrument Co., Ltd., Jinan, China) using the Charpy V-notch test
method (ASTM A370). The microstructures of the samples were characterized on an optical microscope
(DM2500M, Leica Camera AG, Wetzlar, Germany) after mechanical polishing and etching in an 8%
nital solution. The average grain size and martensite lath size were measured with SISC IAS V8.0
image software [17] according to the standard linear intercept method [18]. Five dispersive martensite
packets were chosen to calculate the average martensite lath size.
The morphology of the precipitates was investigated by carbon extraction replica [19] on Cu-grids
and a transmission electron microscope (J EM-2000FX, JEOL, Tokyo, Japan). To obtain the mean size of
precipitates accurately, 100 particles were selected randomly from five pieces of the pictures of 30 µm2
(large visual field) and five pieces of the pictures of 10 µm2 (small visual field).
To capture the conversion points of the martensitic transformation, dilatometric measurements
were conducted on a dilatometer (DIL805A, Baehr, Pirmasens, Germany) using 4 mm diameter × 10 mm
cylindrical specimens. The conversion points of the martensitic transformation were analyzed from
the dilatometry curve using the tangent method [20].
Finally, the lattice distortion of the samples was investigated by X-ray diffraction (DMAX-RB,
Rigaku, Tokyo, Japan) at a step of 0.01◦ and a counting time of 1 s/step using 12 × 12 × 12 mm3
samples. The equilibrium fraction of the precipitates was calculated using Thermo-Calc software
(TCFE7 database, Thermo-Calc Software, Solna, Sweden).

3. Results

3.1. Mechanical Properties

The test results of the mechanical properties are as shown in Table 2. As can be seen, the
nitrogen-alloyed steel can achieve approximately the same toughness as that of nitrogen-free steel,
while the hardness of nitrogen-alloyed steel is about 2 HRC higher than that of nitrogen-free steel.
Especially, the nitrogen-alloy steel can achieve a toughness of 14.3 J·cm−2 and hardness of 49.6 HRC
when tempering at 600 ◦ C for 4 h. The experimental results indicated that nitrogen-alloyed 4Cr5Mo2V
steel can obtain a better match of hardness and toughness with the suitable heat treatment procedure.

Table 2. Mechanical parameters after tempering.

Quenching 1000 ◦ C/0.5 h 1030 ◦ C/0.5 h

Tempering 580 ◦ C/6 h 600 ◦ C/2 h 600 ◦ C/2 h 600 ◦ C/4 h 600 ◦ C/6 h
Nitrogen-alloyed steel/Nitrogen-free steel
Average hardness 1 /HRC 50.2/48.2 49.7/48.1 51.0/48.6 49.6/47.3 48.0/46.0
Average impact toughness 1 (ak/J·cm−2 ) 12.3/12.6 12.5/12.5 12.0/12.3 14.3/14.4 14.6/14.8
1 The experimental errors are ±1 HRC and ±0.5 J·cm−2 for hardness and toughness values.

Nitrogen-alloyed and nitrogen-free steel exhibited different tempering stability, as shown in

Figure 2. As can be seen, the initial hardness of both samples at the quenched state was very similar at
about 54–55 HRC, and the hardness of both decreased continuously with the holding time. However,
the difference was that the hardness of the nitrogen-alloyed steel decreased more slowly than that of
the nitrogen-free steel. After tempering at 600 ◦ C for 8 h, the hardness of the nitrogen-alloyed steel
Metals 2017, 7, 310 4 of 14
Metals 2017, 7, 310 4 of 14

dropped
alloyed to 47
steel HRC while
dropped to 47that
HRC ofwhile
the nitrogen-free steel was 45 HRC,
that of the nitrogen-free which
steel was 45 indicated
HRC, whichthatindicated
nitrogen
improved
that theimproved
nitrogen temper stability of the
the temper steel. of the steel.
stability

Hardnessof
Figure2.2.Hardness oftested
testedsteel
steeltempered
temperedat
at600 ◦ C for various holding times.
600°C
Figure for various holding times.

3.2.
3.2.Martensite
Martensite
Figure
Figure 33 shows
shows the metallographic
metallographicstructure
structureofofthe thesamples
samplessubjected
subjected toto austenitization
austenitization at at ◦C
1030
1030
°C
forfor
30 30
min min followed
followed by tempering
by tempering at 600 ◦
at 600 °C 2for
C for h, 24 h, 4 h and
h and tempering
tempering at 650 ◦
at 650 °C4for
C for h. As4 h.can
Asbe can be
seen,
seen, the microstructures
the microstructures of bothofsamples
both samples are and
are similar similar
mainlyandconsist
mainly of consist
lath-likeofmartensite
lath-like martensite
(marked as
(marked
“M”) as wellas “M”)as a as wellamount
small as a small amount ofaustenite.
of remaining remainingNotably,
austenite. theNotably, the prior
prior austenite austenite
grain boundarygrainis
boundary is visible.
visible. Clearly, Clearly, the
the martensite lathmartensite lath of nitrogen-alloyed
of nitrogen-alloyed steel is much narrower steel isand much narrower
shorter than thatandof
shorter than that of nitrogen-free steel. Moreover, the prior austenite grain
nitrogen-free steel. Moreover, the prior austenite grain size of the two steels is much different. Taking size of the two steels is
much
samples different.
tempered Taking
at 600 ◦ C (2 h)tempered
samples for example,at 600the°C (2 h) for
average prior example,
austenite thegrain
average prior was
diameter austenite
about
grain
15 µmdiameter
and 25 µm was for about 15 µm andsteel
nitrogen-alloyed 25 and
µm nitrogen-free
for nitrogen-alloyed steel and nitrogen-free steel,
steel, respectively.
respectively.
With the increase of tempering temperature or tempering time, the width of the martensite lath
With the
evidently increase
increases, of tempering
indicating temperature
the recovery of theor temperingmatrix.
martensitic time, the width of
However, the martensite
lath-like martensite lath
of
evidently increases,
nitrogen-alloyed indicating
steel exhibits the recovery
a slightly of the martensitic
narrower and shortermatrix. However,
appearance lath-like
than that martensite
of nitrogen-free
of nitrogen-alloyed
steel, when both sets steel exhibitsreceived
of samples a slightlythenarrower and shorter
same subsequent appearance
quenching andthan that oftreatments.
tempering nitrogen-
free
The steel,
coarseningwhenofboth sets of lath
martensite samples received the same
in nitrogen-alloyed steel issubsequent
far less than quenching and tempering
that of nitrogen-free steel.
treatments. The coarsening of martensite lath in nitrogen-alloyed steel
For example, the average thicknesses of martensite lath in steels tempered at 600 C for 4 h wereis far less than ◦
that of nitrogen-
free steel.
about 0.2 For
µm example,
and 0.3 µm thefor
average thicknessessteel
nitrogen-alloyed of martensite lath in steels
and nitrogen-free steel,tempered at 600By°Ccontrast,
respectively. for 4 h
were about0.3
they were 0.2µmµm andand 0.3 µm
0.5µm for nitrogen-alloyed
for nitrogen-alloyed steelsteel and nitrogen-free
and nitrogen-free steel, the
steel when respectively.
samples were By
contrast, they ◦
were 0.3 µm and 0.5µm for nitrogen-alloyed steel and nitrogen-free
tempered at 650 C for 4 h. The coarsening rate of martensite is related to the pinning effect of finer steel when the
samples weresuch
precipitates tempered
as MCatand 650M °C6 Cfor
on4the
h. The coarsening
movement rateboundaries.
of lath of martensite It is
canrelated to the pinning
be deduced that the
effect
additionof finer precipitates
of nitrogen inhibitssuch as MC and
the recovery M6martensitic
of the C on the movement of lath boundaries.
matrix by refining the precipitates It can be
during
deduced that the
the tempering addition
process of nitrogen inhibits the recovery of the martensitic matrix by refining the
[21,22].
precipitates during the tempering process [21,22].
Metals2017,
Metals 2017,7,7,310
310 55ofof14
14

Figure 3. Metallographic images of tested steel after tempering: (a) Nitrogen-free steel (600 ◦ C for 2 h);
Figure 3. Metallographic
(b) nitrogen-alloyed steelimages
(600 ◦ Coffor
tested
2 h); steel after tempering:
(c) nitrogen-free (a) Nitrogen-free
steel (600 steel
◦ C for 4 h); (d) (600 °C for 2
nitrogen-alloyed
h); (b) nitrogen-alloyed steel (600 °C for 2 h); (c) nitrogen-free steel (600 °C for 4 h);
steel (600 C for 4 h); (e) nitrogen-free steel (650 C for 4 h); (f) nitrogen-alloyed steel (650 ◦ C
◦ ◦ (d) nitrogen-
for 4 h).
alloyed steel (600 °C for 4 h); (e) nitrogen-free steel (650 °C for 4 h); (f) nitrogen-alloyed steel (650 °C
3.3. for 4 h).
Precipitates
Previous studies have shown that the properties of steel are closely related to the size, shape,
3.3. Precipitates
and volume fraction of the precipitates [23–28]. Moreover, the added nitrogen has an effect on the
Previous studies have shown that the properties of steel are closely related to the size, shape,
evolution of precipitates at different stages of the heat treatment. Figure 4 shows transmission electron
and volume fraction of the precipitates [23–28]. Moreover, the added nitrogen has an effect on the
microscope (TEM) images of precipitates in the quenched specimens. Clearly, larger amounts of
evolution of precipitates at different stages of the heat treatment. Figure 4 shows transmission
undissolved dispersed carbides were visible in nitrogen-alloyed steel. To investigate the chemical
electron microscope (TEM) images of precipitates in the quenched specimens. Clearly, larger
composition and crystal structure of the precipitates, the undissolved precipitates were analyzed
amounts of undissolved dispersed carbides were visible in nitrogen-alloyed steel. To investigate the
with further calibration of the diffraction spot (lattice constant a = b = c = 0.4154 nm) and chemical
chemical composition and crystal structure of the precipitates, the undissolved precipitates were
analyzed with further calibration of the diffraction spot (lattice constant a = b = c = 0.4154 nm) and
Metals 2017, 7, 310 6 of 14
Metals 2017, 7, 310 6 of 14

composition,
chemical and can beand
composition, identified
can be as V(C, N) with
identified a fccN)
as V(C, crystal
with structure, while
a fcc crystal the precipitates
structure, in
while the
nitrogen-free steel are confirmed as VC (lattice constant a = b = c = 0.4182 nm). Notably, the
precipitates in nitrogen-free steel are confirmed as VC (lattice constant a = b = c = 0.4182 nm). Notably, V(C, N)
particles
the (20particles
V(C, N) nm in diameter)
(20 nm inwere much were
diameter) finer much
than those
finer in nitrogen-free
than steel (50 nm
those in nitrogen-free in diameter).
steel (50 nm in
Apparently,
diameter). Apparently, nitrogen addition is effective to form finer V(C, N) particles, which aretonot
nitrogen addition is effective to form finer V(C, N) particles, which are not easy be
coarsened [29]. Due to high thermal stability, most of the V(C, N) particles could not
easy to be coarsened [29]. Due to high thermal stability, most of the V(C, N) particles could not be be dissolved
during theduring
dissolved heatingthe
stage of thestage
heating quenching process. They
of the quenching may pin
process. Theythemay
prior austenite
pin the priorgrain boundaries
austenite grain
during the heat treatment process, thus refining the prior grains. The precipitation of
boundaries during the heat treatment process, thus refining the prior grains. The precipitation of finer finer V-rich
M(C, N)
V-rich plays
M(C, N)aplays
key role in role
a key ensuring the toughness
in ensuring of the steel.
the toughness of the steel.

Figure 4. Transmission
Figure 4. Transmission electron
electron micrographs
micrographs of
of the
the microstructure
microstructure ofof the precipitates in
the precipitates samples at
in samples at
1030 °C quenching temperature: (a) Nitrogen-free steel; (b) nitrogen-alloyed steel.
1030 ◦ C quenching temperature: (a) Nitrogen-free steel; (b) nitrogen-alloyed steel.

Figure 5 shows the precipitates tempered at 600 ◦°C and 650 °C for 4 h. Obviously, the amount of
Figure 5 shows the precipitates tempered at 600 C and 650 ◦ C for 4 h. Obviously, the amount of
precipitates in the samples is much more than in quenched samples, indicating that many precipitates
precipitates in the samples is much more than in quenched samples, indicating that many precipitates
such as M6C and M23C6 were formed during the tempering process. It is important to note that, in the
such as M6 C and M23 C6 were formed during the tempering process. It is important to note that, in
case of nitrogen-alloyed steel, a uniform distribution of much finer precipitates (ranging from 80 nm
the case of nitrogen-alloyed steel, a uniform distribution of much finer precipitates (ranging from
to 150 nm) occurs compared with the case of nitrogen-free steel (ranging from 100 nm to 200 nm).
80 nm to 150 nm) occurs compared with the case of nitrogen-free steel (ranging from 100 nm to
More remarkable, there are large amounts of dispersed and finer precipitates (average diameter 10
200 nm). More remarkable, there are large amounts of dispersed and finer precipitates (average
nm) identified as V(C, N) in nitrogen-alloyed steel, indicating that the nitrogen addition promoted
diameter 10 nm) identified as V(C, N) in nitrogen-alloyed steel, indicating that the nitrogen addition
the precipitation of vanadium. As can be seen from Figure 5c,d, the mean size of the precipitates
promoted the precipitation of vanadium. As can be seen from Figure 5c,d, the mean size of the
becomes bigger with the increase of tempering temperature, but the coarsening rate of the
precipitates becomes bigger with the increase of tempering temperature, but the coarsening rate of
precipitates in nitrogen-alloyed steel is much slower than that of nitrogen-free steel. Obviously,
the precipitates in nitrogen-alloyed steel is much slower than that of nitrogen-free steel. Obviously,
nitrogen addition inhibited the precipitation and coarsening of the precipitates during the tempering
nitrogen addition inhibited the precipitation and coarsening of the precipitates during the tempering
process. Furthermore, the finer precipitates in the nitrogen-alloyed steel had a stronger pinning effect
process. Furthermore, the finer precipitates in the nitrogen-alloyed steel had a stronger pinning effect
on the movement of the lath boundary, thus decreasing the coarsening of martensite during the
on the movement of the lath boundary, thus decreasing the coarsening of martensite during the
tempering process.
tempering process.
Metals 2017, 7, 310 7 of 14
Metals 2017, 7, 310 7 of 14

Figure 5. Bright-field transmission electron microscopy (TEM) micrographs of precipitates extracted

Figure 5. Bright-field transmission electron microscopy (TEM) micrographs of precipitates extracted
from the specimen tempered at different temperature for 4 h: (a) Nitrogen-free steel (600 °C); (b)
fromnitrogen-alloyed
the specimen steel
tempered at(c)different temperature for (d)
4 h: (a) Nitrogen-free steel ◦
(600 °C); nitrogen-free steel (650 °C); nitrogen-alloyed steel (650 °C).(600 C);
◦ ◦
(b) nitrogen-alloyed steel (600 C); (c) nitrogen-free steel (650 C); (d) nitrogen-alloyed steel (650 C). ◦

3.4. Lattice Distortion

3.4. LatticeSolid-dissolved
Distortion nitrogen in the metallic matrix plays an important role in enhancing the solid
solution strengthening
Solid-dissolved effectinwhich
nitrogen can be reflected
the metallic matrix by the an
plays lattice distortion
important of the
role matrix [30]. the
in enhancing The solid
results of the diffraction angle 2θ measurements from the X-ray diffraction
solution strengthening effect which can be reflected by the lattice distortion of the matrix [30]. (XRD) analysis display
the lattice distortion of the Fe matrix, as shown in Figure 6. It has been definitely confirmed that the
The results of the diffraction angle 2θ measurements from the X-ray diffraction (XRD) analysis display
lattice distortion of the matrix can be characterized by Δd/d% of certain lattice planes [31]. In this
the lattice distortion of the Fe matrix, as shown in Figure 6. It has been definitely confirmed that the
paper, we choose Δd/d% of (110) to evaluate the matrix lattice distortion where d and Δd represent
latticethedistortion
interplanar ofdistance
the matrix (Dm)can andbethe
characterized by ∆d/d%
change of interplanar of certain
distance, lattice planes
resepectively. [31]. is
The result In this
paper,shown
we choose
in Table∆d/d%
3. As canof be
(110) to after
seen, evaluate the heat-treated
the same matrix lattice distortion
process, where
the lattice d and ∆d
distortion of represent
nitrogen the
interplanar
steel is distance (Dm) and
more obvious than the
thatchange of interplanar
of nitrogen-free steel. distance, resepectively.
Additionally, the lattice The resultof
distortion is steel
shown in
Tabletempered
3. As canatbe 600seen,
°C is after
more the
severesamethanheat-treated
that at 650 °C.process, the lattice distortion of nitrogen steel is
more obvious In other
thanwords,
that the diffraction angles
of nitrogen-free of the
steel. tested steelsthe
Additionally, are lattice
shifteddistortion
towards smaller diffraction
of steel tempered at
◦ angles compared to standard
600 C is more severe than that at 650 C. α-Fe. For
◦ example, the lattice plane (110) peaks are located at 44.15° and
44.50° for the nitrogen-alloyed and nitrogen-free steel tempered at 600 °C, respectively, and 44.40°
In other words, the diffraction angles of the tested steels are shifted towards smaller diffraction
and 44.55° for those at 650 °C, respectively although it is located at 44.66° for standard α-Fe [26]. This◦
angles compared to standard α-Fe. For example, the lattice plane (110) peaks are located at 44.15 and
shift
◦ formainly results from an oversaturated body-centered cubic structure ◦of martensite. A smaller
44.50diffraction
the nitrogen-alloyed and nitrogen-free steel tempered at 600 C, respectively, and 44.40◦
angle indicates more bias and more lattice distortion [32]. The high concentration of
and 44.55 ◦ for those at 650 ◦ C, respectively although it is located at 44.66◦ for standard α-Fe [26].
interstitial elements such as C and N in the Fe matrix results in distorting the lattice of ferrite and
This shift mainly resultspeaks
thus the diffraction fromofanferrite
oversaturated
deviate to abody-centered cubic structure
small angle. Apparently, nitrogen of addition
martensite. A smaller
increases
diffraction
the lattice distortion of the matrix, i.e., nitrogen enhances the solid solution strengthening effect of of
angle indicates more bias and more lattice distortion [32]. The high concentration
tempered
interstitial steel. Insuch
elements addition,
as C asandtheNtempering
in the Fetemperature
matrix results increases, the latticethe
in distorting distortion of ferrite
lattice of the Fe and
thus matrix decreasespeaks
the diffraction as theofamount of nitrogen
ferrite deviate to a existing as solid-solution
small angle. Apparently,state decreases,
nitrogen which
addition is
increases
consistent
the lattice with previous
distortion of the research [33]. nitrogen enhances the solid solution strengthening effect of
matrix, i.e.,
tempered steel. In addition, as the tempering temperature increases, the lattice distortion of the
Fe matrix decreases as the amount of nitrogen existing as solid-solution state decreases, which is
consistent with previous research [33].
Metals 2017, 7, 310 8 of 14
Metals 2017, 7, 310 8 of 14

Figure 6. X-ray
Figure diffraction
6. X-ray result
diffraction resultshowing
showing the latticedistortion
the lattice distortionofof tested
tested steels
steels quenched
quenched °C ◦ C
at 1030
at 1030
and tempered
and tempered at 600 ◦
at 600C°C and
and 650 ◦
650 C°Cfor
for44 h.
h.

TableTable 3. Lattice distortion of samples quenched at 1030◦°C for 0.5 h and tempered at 600 °C
3. Lattice distortion of samples quenched at 1030 C for 0.5 h and tempered at 600 ◦ Cand 650 ◦
and 650 C,
°C, respectively, for 4.0 h. (Dm: Interplanar distance.)
respectively, for 4.0 h. (Dm: Interplanar distance.)
Tempering Standard Dm
Samples Mean Dm (Å) Change (Δd/d%)
Temperature
Tempering (°C) (Å)
Samples 600 (◦ C)
Nitrogen-free Temperature Standard
2.027Dm (Å) Mean
2.043 Dm (Å) Change (∆d/d%)
0.79
Nitrogen-alloyed 600 2.027 2.064 1.82
Nitrogen-free
Nitrogen-free
600
650
2.027
2.027 2.037
2.043 0.50
0.79
Nitrogen-alloyed
Nitrogen-alloyed
600
650
2.027
2.027 2.056
2.064 1.43
1.82
Nitrogen-free 650 2.027 2.037 0.50
Nitrogen-alloyed 650 2.027 2.056 1.43
4. Discussion

4. Discussion
4.1. Effect of Nitrogen on Precipitates
Experimental results show that nitrogen alloyed in steel affects the precipitation and dissolving
4.1. Effect of Nitrogen on Precipitates
reaction of the tested steel significantly. The equilibrium formation of precipitates in steels was
investigated
Experimental using Thermo-Calc
results show that thermodynamic
nitrogen alloyed software (TCFE7
in steel database,
affects Thermo-Calcand
the precipitation Software,
dissolving
reaction of the tested steel significantly. The equilibrium formation of precipitates database
Solna, Sweden), as shown in Figure 7. The type of carbide is defined in the Thermo-Calc in steels was
accordingusing
investigated to itsThermo-Calc
stoichiometricthermodynamic
formula. As can software
be seen from(TCFE7Figures 7a,b, complex
database, and varied
Thermo-Calc Software,
carbides such as MC-type, M6C-type M7C3-type and M23C6-type precipitated at different temperatures
Solna, Sweden), as shown in Figure 7. The type of carbide is defined in the Thermo-Calc database
in both samples, which is consistent with prior research [34–36]. To simplify issues here, two
according to its stoichiometric formula. As can be seen from Figure 7a,b, complex and varied carbides
important temperatures (quenching temperature 1030 °C and tempering temperature 600 °C) were
suchchosen
as MC-type,
to analyzeM6the
C-type M7 C3 -type
precipitation of twoandsamples
M23 C6during
-type precipitated
the quenchingatand different
temperingtemperatures
process. in
bothMost
samples,
of thewhich is consistent
precipitates with prior
are dissolved research
in matrix during[34–36]. To simplify
the heating stage of issues here, two
the quenching important
process
temperatures (quenching temperature 1030 ◦ C and tempering temperature 600 ◦ C) were chosen to
(1030 °C), except for a certain amount of MC-type carbides which are the most important
analyze the precipitation
strengthening carbides.of two samples
However, duringthat
it is apparent thethe
quenching
amount ofand tempering
undissolved MCprocess. Most of the
in the nitrogen-
alloyed steel
precipitates are (0.5%) is greater
dissolved than that
in matrix of nitrogen-free
during the heatingsteel (0.2%).
stage of This
the suggests
quenching thatprocess (1030 ◦ C),
the mergence
of nitrogen
except into MC
for a certain amountis conducive to thecarbides
of MC-type nucleation of MC
which areresulting
the most in important
a larger amount. Furthermore,
strengthening carbides.
the main elements of MC were also investigated. As shown in Figures 7c,d, MC
However, it is apparent that the amount of undissolved MC in the nitrogen-alloyed steel (0.5%) is exists mainly as VC
in the nitrogen-free steel and as V(C, N) in nitrogen-alloyed steel. The reason may be that both C and
greater than that of nitrogen-free steel (0.2%). This suggests that the mergence of nitrogen into MC is
N are available to form V-rich carbonitrides. It can be seen that the solid solution temperature of V(C,
conducive to the nucleation of MC resulting in a larger amount. Furthermore, the main elements of MC
N) in the nitrogen-alloyed steel is 1300 °C while that of VC is 1050 °C. This signifies that the
were also investigated. As shown in Figure 7c,d, MC exists mainly as VC in the nitrogen-free steel and
as V(C, N) in nitrogen-alloyed steel. The reason may be that both C and N are available to form V-rich
carbonitrides. It can be seen that the solid solution temperature of V(C, N) in the nitrogen-alloyed steel
is 1300 ◦ C while that of VC is 1050 ◦ C. This signifies that the incorporation of nitrogen into MC could
Metals 2017,
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7, 310
310 99 of
of 14
14

incorporation of nitrogen into MC could lead V(C, N) to exist at higher temperature and thus impose
lead V(C, N)
important to exist
effects at higherthe
on refining temperature and thus
prior austenitic impose important effects on refining the prior
grains.
austenitic grains.
Subsequently, during the tempering treatment at 600 °C, a large amount of carbides such as
◦ C, a large amount of carbides such as
M23CSubsequently, during in
6 and M6C precipitate theboth
tempering
samples,treatment
and thereatis 600 no distinct difference in the amount of these
M C
carbides
23 6 and M C
for the precipitate in both samples, and there is no
6 two tested steels. However, a subtle change of chemical distinct difference in the amount
composition occursoftothese
MC
carbides for the two tested steels. However, a subtle change of chemical composition
of nitrogen-alloy steel. As shown in Figures 7c,d, the fraction of N atoms in V(C, N) decreases occurs towith
MC
of
thenitrogen-alloy steel. of
increasing fraction AsC,shown in Figure
indicating 7c,d, the
that some fraction
of the C atomsof Ninatoms in V(C,
the matrix N) decreases
would displace thewith
N
the increasing fraction of C, indicating that some of the C atoms in the matrix
atoms of V(C, N) and most of the N would be as solid-dissolved in the matrix at 600 °C. N atoms and would displace the N
atoms of suppress
V(C, N) and ◦ C. N atoms and
C atoms themost of the of
dispersion N one
would be as in
another solid-dissolved
the process ofinthe thedisplacement
matrix at 600reaction, and thus
C atoms suppress the dispersion of one another in the process of the displacement
in refining the precipitates. Further, the solid-dissolved nitrogen in tempered steels would cause reaction, and thus
in refining the precipitates. Further, the solid-dissolved nitrogen in tempered steels would
lattice distortion of the matrix, playing an important role in solution strengthening. The solid solution cause lattice
distortion
of nitrogenofcan thebe
matrix, playing
observed an important
by XRD, as shown role in solution
in Figure 6. strengthening. The solid solution of
nitrogen can be observed by XRD, as shown in Figure 6.

Figure 7.7.Equilibrium
Figure Equilibriumprecipitation
precipitation calculated
calculated by Thermo-Calc
by Thermo-Calc software
software for various
for various carbidescarbides in
in samples
samples
(W: Weight(W:percent
Weight inpercent in yNitrogen-free;
y axis): (a) axis): (a) Nitrogen-free; and (b) nitrogen-alloyed
and (b) nitrogen-alloyed steel;
steel; and for and for the
the elements of
elements
the of the (c)
MC carbide MCnitrogen-free;
carbide (c) nitrogen-free; (d) nitrogen-alloyed
(d) nitrogen-alloyed steel. steel.

4.2. Effect
4.2. Effect of
of V(C,
V(C, N)
N) on
on Refining
Refining Prior
Prior Austenitic
Austenitic Grains
Grains
The finer
The finer grains
grains could
could not
not only
only improve
improve the the hardness
hardness ofof the
the steel
steel but
but also
also guaranteed
guaranteed toughness.
toughness.
Obviously, the effect of nitrogen on refining the grains plays an important
Obviously, the effect of nitrogen on refining the grains plays an important role in role in obtaining
obtaining optimum
optimum
strengthand
strength andtoughness.
toughness.The The experimental
experimental results
results revealed
revealed thatgrain
that the the grain refinement
refinement of nitrogen-
of nitrogen-alloyed
steel is related to the precipitation of a much finer dispersion of the V(C, N) during theduring
alloyed steel is related to the precipitation of a much finer dispersion of the V(C, N) reheatingthe
reheatingThis
process. process. Thispinning
stronger strongereffect
pinning
caneffect can be interpreted
be interpreted in terms in ofterms of classical
classical pinningpinning
theory intheory
that
in that the effect of precipitates on pinning the austenitic grain boundary is mainly
the effect of precipitates on pinning the austenitic grain boundary is mainly related to the size and related to the size
and number of the precipitates and the interface structure between the austenite
number of the precipitates and the interface structure between the austenite matrix and the precipitates. matrix and the
precipitates.
The The effect
effect of nitrogen onof nitrogen
refining theon refining
prior the prior
austenitic grainsaustenitic grains could
could be estimated be process
in the estimated in the
as below.
process as below. The required parameters of VC and V(C, N) are shown
The required parameters of VC and V(C, N) are shown in Table 4. The lattice constant and diameter in Table 4. The lattice
constant and
parameter diameter
of the VC and parameter of the VCare
V(C, N) particles and V(C, N) from
analyzed particles
TEMare analyzed
images from
of the TEM images
precipitates of
of the
the precipitates
quenched of the
samples. Thequenched
volume samples.
fraction f,The
of VCvolume fraction
and V(C, f, of VC
N) was and V(C,
calculated byN)thewas calculated
Thermo-Calc
by the Thermo-Calc software, valued as 0.68% and 0.21% for nitrogen-alloyed steel
software, valued as 0.68% and 0.21% for nitrogen-alloyed steel and nitrogen-free steel, respectively. and nitrogen-free
steel, respectively.
Metals 2017, 7, 310 10 of 14

Table 4. Parameters of VC and V(C, N) in the tested samples.

Precipitates Lattice Constant (nm) Average Diameter 1 (nm) Volume Fraction (f )

VC 0.4182 50 0.21%
V(C, N) 0.4154 20 0.68%
1 The standard deviation values of diameter are 10 nm and 8 nm for VC and V(C, N).

The behavior of MC during the heating process is closely related to lattice misfit and the interfacial
energy of the MC/matrix system. The lattice misfit parameter δ which is defined as the relative
difference of lattice width can be obtained as follows [37]:
 
 M(C, N) − aγ 
a 
δ= , (1)
 aM(C, N) 

aγ = 0.36468 × [1 + 21.1 × 10−6 ( T − 912)] + 0.0033[C], (2)

where aM(C, N) and aγ are the lattice constants of M(C, N) and austenite, respectively. T is temperature
and [C] is carbon content in the matrix. The lattice constants of M(C, N) are valued as 0.4182 nm and
0.4154 nm for VC and V(C, N), respectively. The interface energy, σ, of a semi-coherent interface [37]
can be calculated from Equations (3)–(5):

Eγ aγ
σ= √ , (3)
4 2π (1 − ϑ2 )

Eγ = 254680 − 114.76T, (4)

!
1 2
f (δ) = δ ln + , (5)
2δ 1 + 12
4δ
where Eγ is Young’s modulus, which can be calculated from Equation (4), ϑ is the Poisson ratio of
austenite, valued as 0.32. The maximum encumbrance force, Fm , of grain boundary pinning exerted by
second-phase particles [37] can be obtained using Equation (6):

3fσ
Fm = , (6)
2r
where r is the mean radius of MC, and valued as 25 nm and 10 nm for VC and V(C, N), respectively.
The following result was obtained as shown in Table 5. It can be seen from the calculation that the
incorporation of N into MC precipitates leads to a decrease in the interfacial energy of the MC/Fe
matrix system. This suggests that the addition of nitrogen decreases the lattice misfit and the interfacial
energy of MC with the austenite matrix and thereby hinders the movement of the austenite grain
boundary efficiently. According to estimates, the contribution of V(C, N) on refining grains is 7.8 times
of that of VC. i.e., nitrogen addition increases the grain refining efficiency of VC by 6.8 times. This
result offers sound explanations as to why the size of prior austenitic grains in nitrogen-alloyed steel is
smaller than in that of nitrogen-free steel. Comprehensive reasons for this inhibition ability may be
that nitrogen addition not only increases the amount of MC carbides but also causes these carbides to
be much finer and dispersed.

Table 5. Thermodynamic calculation results.

Precipitates Lattice Mismatch (100%) Interface Energy (J/m2 ) F m (N/m2 ) F m(V(C, N)) /F m(VC)
VC 0.1182 0.4449 5.6 ×104
7.8
V(C, N) 0.1122 0.4338 4.4 × 105
 Table 5. Thermodynamic calculation results.

Lattice Mismatch
Precipitates Interface Energy (J/m2) Fm (N/m2) Fm(V(C, N))/Fm(VC)
(100%)
VC 0.1182 0.4449 5.6 × 10 4
Metals 2017, 7, 310 7.8 11 of 14
V(C, N) 0.1122 0.4338 4.4 × 10 5

4.3. Effect of Nitrogen on Martensitic Transformation

Transformation
As is well known, added nitrogen has an effect on martensitic transformation [38]. The specific
martensite is bigger
volume of martensite bigger thanthan that
that of
of austenite,
austenite, an an approximately
approximately volume
volume expansion which is
characterized by ∆l/l can be obtained when the martensite transformation is inducedis
characterized by Δl/l can be obtained when the martensite transformation induced
from from
supercooled
supercooled
austenite [39]. austenite
Therefore,[39]. Therefore,
transition transition temperatures
temperatures of martensiteofcan martensite
be obtained can from
be obtained from the
the dilatometric
dilatometric
curves by thecurves
tangentbymethod.
the tangent method.
As shown As shown
in Figure in Figure
8, as the 8, as the
nitrogen-free samplenitrogen-free sample
is cooled at the rateis
cooled ◦ at the rate of 25 °C/s, there is an abrupt◦ change ◦from 310 °C
of 25 C/s, there is an abrupt change from 310 C to 250 C representing the martensite formation to 250 °C representing the
martensite
process in theformation
tested process in the tested
steel. Therefore, MS steel.
and M Therefore, MS and Mf ofsteel
f of the nitrogen-free the nitrogen-free
can be inferred steeltocan
be
be ◦ C and to
310inferred be◦310
250 °C and 250 °C,
C, respectively. respectively.
While, MS and While,
Mf are M 280 ◦ C and
S and Mf are ◦ C°C
175280 forand 175 °C for nitrogen-
nitrogen-alloyed steel,
alloyed steel,Clearly,
respectively. respectively.
nitrogen Clearly,
addition nitrogen
decreases addition decreases
the transition the transition
temperature temperature
of martensitic of
greatly,
martensitic greatly, increasing
increasing transformation transformation
resistance resistance
of martensitic. of martensitic.
In other In other words,
words, hardenability washardenability
significantly
was significantly decreased by nitrogen. Remarkably, the decrease
decreased by nitrogen. Remarkably, the decrease of MS may increase the volume fractionthe of M S may increase volume
of retained
austenite, as shown in Figure 9. It is observed that the microstructure of both samples exhibitsof
fraction of retained austenite, as shown in Figure 9. It is observed that the microstructure both
typical
samples exhibitswhile
lath martensite, typical lath
the martensite,
film-like while
retained the film-like
austenite between retained austenite
martensitic lathbetween martensitic
in nitrogen-alloyed
lath in nitrogen-alloyed steel is more than that of nitrogen-free steel. Retained
steel is more than that of nitrogen-free steel. Retained austenite in the microstructure can improve austenite in the
microstructure can improve
resistance to impact fatigue by theinhibiting
resistancetheto initiation
impact fatigue by inhibiting
and growth of fatigue thecrack,
initiation
and and growth
increase the
of fatigue crack,
toughness of theand
steelincrease the toughness
[40]. However, owning of to
theitssteel [40]. However,
relatively owning
small volume to its relatively
fraction, small
the diffraction
volume
peak fraction, the
of austenite diffraction
cannot be detected peakbyof XRD
austenite
shown cannot be detected
in Figure 6. by XRD shown in Figure 6.

8. Transition
Figure 8. Transition temperatures
temperatures of
of samples
samples steels
steels during
during quick
quick cooling
cooling treatment
treatment (Δl
(∆l and
and l are
expansion length and original length of samples, respectively).

Figure
Figure 9.9.TEM micrographs
TEM of retained
micrographs austenite
of retained in samples
austenite temperedtempered
in samples at 600 °C for
at 4600
h: (a)
◦ CNitrogen-
for 4 h:
free steel; (b) nitrogen-alloyed steel.
(a) Nitrogen-free steel; (b) nitrogen-alloyed steel.
Metals 2017, 7, 310 12 of 14

5. Conclusions
From the above-described experiment and theoretical analysis, the key points can be summarized
as follows:

(1) Nitrogen addition can increase hardness and temperability of 4Cr5Mo2V steel without toughness
loss with a reasonable heat treatment procedure. The fair match of strength and high toughness
of the nitrogen-alloyed 4Cr5Mo2V steel is associated with the refinement of the prior austenite
grain size, the solution hardening of nitrogen atoms after tempering, and the increase of
retained austenite.
(2) During the heating stage of the quenching process, nitrogen promoted the precipitation of
vanadium as finer V(C, N), imposing a stronger effect on restricting the growth of prior austenitic
grains than VC and increasing grain refining efficiency of VC by 6.8 times. During the quenching
process, the nitrogen decreases the MS of the martensitic transformation, increasing retained
austenite which is a benefit for toughness.
(3) In the process of tempering, some of the N atoms in M(C, N) were dissolved in the matrix,
causing crystal lattice distortions, thus boosting the solution reinforcing effect. Meanwhile,
the solid-dissolved nitrogen inhibits the diffusion of carbon, decreasing the growth rate of the
carbides, and increasing tempering resistance.

Acknowledgments: The authors acknowledge financial support from the National Natural Science Foundation
of China (Grant No. U1660114 and Grant No. U51174026).
Author Contributions: Jinbo Gu and Jingyuan Li conceived and designed the experiments; Jinbo Gu performed
the experiments; Jinbo Gu and Jingyuan Li analyzed the data; Yulai Chen was responsible for language
modification; Jingyuan Li contributed reagents/materials/analysis tools; Jinbo Gu wrote the paper.
Conflicts of Interest: The authors declare no conflict of interest.

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