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Suppression of Austenite Grain Coarsening by Using Nb–Ti Microalloying in

High Temperature Carburizing of a Gear Steel

Article in Advanced Engineering Materials · June 2019

DOI: 10.1002/adem.201900132

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Austenite Grain www.aem-journal.com

Suppression of Austenite Grain Coarsening by Using

Nb–Ti Microalloying in High Temperature Carburizing of
a Gear Steel
Xiaoxue An,* Yong Tian,* Haojie Wang, Yongfeng Shen, and Zhaodong Wang

carburizing time of some heavy-duty gears

Austenite grain coarsening behavior during pseudo-carburizing is investigated is even longer.[4] Technological advances in
in a 18CrNiMo7-6 steel, Nb microalloyed, and Nb–Ti microalloyed the field of carburizing, evolving from
18CrNiMo7-6 steels, which are designed to evaluate the effects of Nb–Ti conventional gas carburizing to vacuum
and plasma carburizing, would allow the
microalloying on suppressing austenite grain growth at elevated temperatures
carburizing time to be significantly re-
appropriate to high temperature carburizing operations. Pseudo-carburizing duced by operating at higher temper-
heat treatments, without carburizing atmosphere, are performed in the atures.[5–8] Carburizing above 930
C is
temperature range of 850–1150
C for 0.5–8 h. Transmission electron micros- usually called high-temperature carburiz-
copy (TEM) incorporated with EDS spectra is used to investigate the ing. Additionally, the carburizing process is
mainly restricted by the diffusion process,
morphology and size distributions of precipitates in pseudo-carburized
and the diffusion coefficient is a function of
specimens. The results show that Nb–Ti microalloying has an obvious temperature. Therefore, there is increas-
advantage in restraining austenite grain growth and increasing the grain ingly interest in the development of a new
coarsening temperature. Even in the temperature range of 1000–1150
C, Nb– generation of gear steels for high tempera-
Ti microalloyed steel produces fine and uniform grain structures. The fine ture carburizing because it can remarkably
grain sizes observed in Nb–Ti microalloyed steel are attributed to the pinning shorten the carburizing time and improve
productivity.[9] It has been reported that the
effect of Nb–Ti precipitates that hinder austenite grain coarsening. The key
carburizing time can be reduced by up to
reason for the significant difference of grain growth mechanisms between the 60% as the carburizing temperature
base steel and Nb–Ti microalloyed steel is because Nb–Ti microalloying changes from 950 to 1050
C at the
changes grain growth kinetic of the base steel. The results indicate that Nb– identical carburized layer depth.[10] How-
Ti microalloying can be successfully used to suppress grain growth in gear ever, high temperature carburizing would
result in obvious grain coarsening in most
steels for high temperature carburizing.
of current commercial gear steels due to
either primary or abnormal grain
growth.[11,12] Thus, optimizing precipitate
distributions with adding microalloy such as Nb, V, Ti, and Al is
1. Introduction increasingly applied to suppress austenite grain coarsening
during carburizing in the past years.[13–17]
Gear steels are widely used in many diverse fields, such as Previous investigations have utilized various microalloy
automobile manufacturing, petrochemical, and mining machin- additions to modify different conventional gear steels with the
ery. The carburizing is mainly applied to satisfy the demand of a aim of elevating carburizing temperatures. However, the
wear-resistant surface with a suitable tough core for gears.[1,2] In occurrence of abnormal grain growth in the modified steels
conventional gas carburizing processing, carburizing is typically presents an inevitable obstacle on this topic in recent years. The
conducted at 930
C for times from several hours to a few days coarsening of microalloy precipitates in austenite is thought to
depending on the desired properties of case surface.[3] The be the controlling factor in the onset of abnormal grain growth,
and solute drag is assumed to be of secondary significance.[18]
Dr. X. X. An, Prof. Y. Tian, Dr. H. J. Wang, Prof. Y. F. Shen, To date, numerous researches have explored the feasibility
Prof. Z. D. Wang and extent of using Nb or Ti microalloying to limit unacceptable
State Key Laboratory of Rolling and Automation austenite grain growth of gear steels during high temperature
Northeastern University carburizing.[19–23] However, Nb or Ti microalloying alone has
Shenyang 110819, P. R. China
E-mail: 15140110204@163.com; tianyong@ral.neu.edu.cn
limited effect on suppressing austenite grain coarsening of gear
steels, especially at temperatures above 1000
C. Since a similar
The ORCID identification number(s) for the author(s) of this article mechanism may be applicable to Nb–Ti microalloying, it is
can be found under https://doi.org/10.1002/adem.201900132.
worthwhile to further investigate the synergistic effect of Nb–Ti
DOI: 10.1002/adem.201900132 microalloying on increasing the grain coarsening temperature of

Adv. Eng. Mater. 2019, 21, 1900132 1900132 (1 of 10) © 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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gear steels. Nb–Ti microalloying was taken into consideration
because of its potential to form a more stable grain refiner (Nb,
Ti)C precipitates. On the other hand, few systematic studies aim
to provide the necessary fundamental information about the
mechanism how Nb–Ti microalloying can inhibit the austenite
grain coarsening of gear steels during high temperature
carburizing above 1000
C.
18CrNiMo7-6 steel is widely used because of its excellent
comprehensive performance. The application of 18CrNiMo7-6
steel is concentrated in the production of wind power, mine
reducer, and high speed locomotive gears and parts that require
surfaces hardened by thermal treatment after forging.[24] It
usually requires deep carburization, but at present there is less
research on high temperature carburization of 18CrNiMo7-6
steel. Therefore, this investigation focused on 18CrNiMo7-6
case-hardening steel. Experimental alloys were developed to
assess the ability of Nb–Ti microalloying to suppress austenite
grain coarsening at elevated temperatures.
The microalloying strategy of this study was using carbide
rather than nitride precipitation to provide grain coarsening
resistance. As Ti:N ratio close to stoichiometric is 3.42 by weight,
Ti added stoichiometrically to the Nb microalloyed 18CrNiMo7-6
steel will precipitate N as TiN. And the remaining Ti and Nb will
precipitate as (Nb, Ti)C.
According to the previous work, additions of 0.06 wt.% Nb
appear to provide the best potential for grain growth inhibition
during high temperature carburizing.[21] Furthermore, in order
to reduce the risk of large, cuboid inclusions, it is better to keep
the N as low as possible to minimize the volume fraction of TiN-
based compounds in the steel. Similarly, the amount of Ti may
be able to use in continuously-cast steels without generating
excessive large TiN particles is on the order of approximately
0.02 wt.% Ti.[25]
To further utilize the grain coarsening resistance effect of Nb–
Ti microalloying in engineering materials, the mechanisms of
Nb–Ti microalloying additions affecting the composition and
size evolution of precipitates require further definition.
Therefore, this work mainly focus on the austenite grain
coarsening behavior of Nb–Ti microalloyed steel compared to Nb
microalloyed steel and the base steel, which were designed for
carburized gears. The present interest was to quantify and
elucidate the effect of Nb–Ti microalloying on precipitate and
grain size evolution.
Figure 1. Thermo-Calc simulations of the designed microalloyed steels (a) 0.06 Nb microalloyed steel (b) 0.06Nb-0.02Ti microalloyed steel.
Adv. Eng. Mater. 2019, 21, 1900132 1900132 (2 of 10)
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2. Experimental Section
Based on the thermodynamic calculations, two microalloyed
steels were designed. Thermo–Calc simulations of the designed
microalloyed steels are shown in Figure 1. TiN precipitates are
stable even at temperatures above 1250
C, whereas the amount
of NbC and (Nb, Ti)C precipitates would decrease with the
increasing temperature. Additionally, even with the addition of
only 0.02 wt.% Ti, the amount of (Nb, Ti)C precipitates in the
Nb–Ti microalloyed steel is much higher than that of NbC in the
Nb microalloyed steel at the same temperatures (>1000
C).
Consequently, three experimental steels were refined in a
vacuum induction furnace and then cast into ingots. Homoge-
nization was conducted on the ingots to make the microalloying
elements dissolved evenly in the steels. Subsequently, the ingots
were reheated to 1200
C for 2 h, forged to bars of 60 and 30 mm
in diameter. The chemical compositions of three experimental
steels are shown in Table 1. The billets of the three steels were
reheated to 1250
C for 2 h and then forged to bars of 30 mm in
diameter because of the presence of slight microsegregation.
Metallographic specimens were cut from the billets in order to
observe the microstructures of the steels until there was no
microsegregation. Finally, the specimens of 25 mm in diameter
and 5 mm in thickness were machined from the forged bars.
High temperature laser-scanning confocal microscopy was
used to observe the austenite grain growth of the three steels
holding at 1000
C for 30 min. The specimens of the base steel
were pseudo-carburized (i.e., austenitized in a non-carburizing
atmosphere) at temperatures of 850, 900, 930, 960, 1000, 1050,
1100, and 1150
C, followed by water quenching. The specimens
of Nb–Ti microalloyed steel and Nb microalloyed steel were
pseudo-carburized at temperatures of 850, 950, 1000, 1050, 1100,
and 1150
C, followed by water quenching. The pseudo-
carburizing treatments were performed for 0.5, 1, 2, 4, and
8 h, respectively.
The austenite grain boundaries of the pseudo-carburized
specimens were revealed by etching in an oversaturated aqueous
solution of picric acid. The size of the austenite grains was
examined by optical micrographs. The mean austenite grains
size was measured by the “Mean Line Intercept Method” as
reported in ASTM standard E112.[26]
Transmission electron microscopy (TEM) was used to observe
the precipitates in the selected pseudo-carburized specimens
© 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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Table 1. Chemical composition of three experimental steels (mass fraction/%).

Steel C Si Mn Cr Ni Mo P S N Nb Ti
No. 1 0.17 0.2 0.60 1.65 1.74 0.35 0.0037 0.0058 0.0019 0.002 0.001
No. 2 0.17 0.18 0.60 1.74 1.48 0.33 0.0042 0.0068 0.0028 0.059 0.001
No. 3 0.19 0.22 0.56 1.48 1.63 0.32 0.0038 0.0034 0.0014 0.062 0.026

and to evaluate their size, morphology, and distribution.
Qualitative chemical analysis of the precipitates was determined
by energy dispersive spectroscopy (EDS) analysis. In this work,
the specimens of TEM were selected based on austenite grain
coarsening behavior observed in optical microscopy.
For each sample evaluated in the TEM, the sizes of
precipitates were measured individually from the micrograph
obtained from different fields of view by using the image analysis
software of Image-Pro Plus. In order to accurately characterize
the size distribution of precipitates used to suppress abnormal
grain growth, precipitates larger than 100 nm were excluded
from measurement because of the lack of pinning force.[19]
3. Results and Discussion
3.1. Effect of Temperature on Austenite Grain Coarsening
Behavior
Figure 2 presents a series of optical micrographs arranged to
facilitate direct comparisons of the effects of Nb and Nb–Ti
microalloying on austenite grain coarsening behavior after
pseudo-carburizing at different temperatures for 1 h. Figure
2(a–d) represent grain coarsening behavior in the base steel
pseudo-carburized at 900, 930, 960, and 1000
C for 1 h . Figure 2
(e–h) and (i–l) represents austenite grain coarsening behavior in

Figure 2. Optical micrographs showing austenite grain structures for various steels after pseudo-carburizing at different temperatures for 1 h (a) the
base steel, 900
C (b) the base steel, 930
C (c) the base steel, 960
C (d) the base steel, 1000
C (e) Nb microalloyed steel, 1000
C (f) Nb microalloyed
steel, 1050
C (g) Nb microalloyed steel, 1100
C (h) Nb microalloyed steel, 1150
C (i) Nb–Ti microalloyed steel, 1000
C (j) Nb–Ti microalloyed steel,
1050
C (k) Nb–Ti microalloyed steel, 1100
C (l) Nb–Ti microalloyed steel, 1150
C.

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the Nb microalloyed steel and Nb–Ti microalloyed steel pseudo-
carburized at 1000, 1050, 1100, and 1150
C for 1 h, respectively.
The micrographs show that the increase in pseudo-carburiz-
ing temperature changed the austenite grain structure from a
fine uniform grain structure to a bimodal structure. Austenite
grain structure of the base steel was fine and uniform below
960
C and had a characteristic of normal grain growth mode
with a very large mean grain size of 101 mm at 1000
C. In
comparison to the base steel, Nb microalloying and Nb–Ti
microalloying effectively inhibited austenite grain coarsening of
the steels during pseudo-carburizing at 1000
C. Abnormal grain
growth was observed in the Nb microalloyed steel pseudo-
carburized at temperatures between 1050 and 1100
C. However,
the grains grew normally again at 1150
C and had a very large
mean grain size of 197 mm. Austenite grain structure of the Nb–
Ti microalloyed steel was fine with the mean grain size of 26 mm
and uniform at 1100
C but became obviously coarsened once to
1150
C. Therefore, grain coarsening temperatures of the three
experimental steels were 960, 1050, and 1150
C, respectively.
There was a remarkable influence of Nb–Ti microalloying and
Nb microalloying in the development of new generation steels
for high temperature carburizing with improved resistance to
abnormal grain growth.
The effects of microalloying on austenite grain growth reflect
competition between the driving forces for normal/abnormal
grain growth and pinning forces of exerted precipitates.
Precipitates commonly dissolve and/or coarsen after high
temperature carburizing and consequently austenite grain
boundaries are partially unpinned. If the condition of unpinning
for some grains occurs while others are still pinned, abnormal
grain growth begins to develop in a narrow temperature/time
range.[22] Temperature primarily alter the conditions for the
onset of abnormal grain growth as the coarsening of micro-
alloying precipitates in austenite is thought to be the controlling
factor.[25] The onset of abnormal growth is associated with the
grain coarsening temperature. In this study, the casting process,
processing history, and pseudo-carburizing conditions were
essentially identical for all the steels except alloy content. Since
the N addition was few and TiN dispersion had a low solubility in
austenite, it was considered that the TiN distribution developed
primarily during the initial casting and hot rolling procedures.
Figure 3. Mean austenite grain size versus holding time of the three steels after pseudo-carburizing at different temperatures (a) the base steel, (b) Nb
microalloyed steel, (c) Nb–Ti microalloyed steel.
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The characteristic of TiN dispersion was considered to have little
effect on grain growth during pseudo-carburizing treatments.
Therefore, the differences in the grain-coarsening temperatures
of three experimental steels were attributed to the presence of
Nb-rich and Nb–Ti precipitates. Nb–Ti microalloying was more
effective than Nb microalloying in increasing the grain
coarsening temperature compared to other conditions. Overall,
the micrographs illustrated the huge potential of Nb–Ti
microalloying in reducing the susceptibility to abnormal grain
growth in steels subjected to carburizing temperatures higher
than 1000
C.
3.2. Effect of Time on Austenite Grain Coarsening Behavior
In order to quantify the effects of holding time on austenite grain
coarsening behavior, the mean austenite grain size were
measured and the results are summarized in Figure 3 and 4.
Figure 3(a–c) represents the relationship between holding
time and the mean austenite grain size for a specific alloy/
temperature combination. Austenite grains of the base steel
grew slowly at 900
C. At 930–960
C, grain sizes increased
slightly with an increase in holding time. When the pseudo-
carburizing temperature was 1000
C, grains grew rapidly and
exhibited larger mean austenite grain size. Therefore, the base
steel is not suitable for high temperature carburizing above
1000
C. For Nb microalloyed steel, austenite grains were fine
at 1000
C and grew slowly at 1050–1100
C while the holding
time was less than 2 h, but rapidly at 1150
C. Meanwhile,
austenite grains of the Nb–Ti microalloyed steel grew slowly at
1000–1100
C within 8 h and exhibited smaller mean austenite
grain size than the corresponding Nb microalloyed steel. In
contrast, austenite grain structures with very large mean grain
sizes (42, 43, 73, 69, and 75 mm) were observed at 1150
C for
all examined durations. Pseudo-carburizing the Nb micro-
alloyed steel at 1000
C and Nb–Ti microalloyed steel at
1100
C, for all the examined durations, produced fine and
uniform austenite grain structures. That is to say, Nb
microalloyed steel is suitable for high temperature carburiz-
ing below 1000
C while Nb–Ti microalloyed steel below
1100
C.
© 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.advancedsciencenews.com
Figure 4. Mean austenite grain size versus holding time of the three steels after pseudo-carburizing at (a) 1000
C, (b) 1050
C, (c) 1100
C, (d) 1150
C.
Figure 4(a–d) represents the relationship between holding
time and the mean austenite grain size of three steels holding at
1000, 1050, 1100, and 1150
C, respectively. Microalloyed steels
had little change in austenite grain size as pseudo-carburizing
temperature was 1000
C. However, the austenite grain size of
the base steel increased significantly with the holding time. The
mean austenite grain sizes of the base steel and Nb–Ti
microalloyed steel did not change much with the holding time
as the pseudo-carburizing temperatures were 1050 and 1100
C,
The mean austenite grain size of the base steel was much larger
than that of the Nb–Ti microalloyed steel. Whereas the austenite
grains of the Nb microalloyed steel grew rapidly when the
holding time was longer than 2 h. As the pseudo-carburizing
temperature was 1150
C, austenite grain sizes of the base steel
and Nb–Ti microalloyed steel gradually increased from 140 to
174 mm and 42 to 74 mm, then became stable after the holding
time exceeding 2 h. However, the austenite grain size of Nb
microalloyed steel increased rapidly and was much larger than
that of the base steel and Nb–Ti microalloyed steel when the
holding time was longer than 0.5 h.
Figure 4 reveals that Nb microalloying and Nb–Ti micro-
alloying had the similar effect on austenite grain coarsening
behavior when the pseudo-carburizing temperature was
1000
C. With the increase of pseudo-carburizing temperature
and holding time, the effect of Nb microalloying on suppressing
austenite grain coarsening significantly reduced. Austenite grain
sizes in Nb microalloyed steel were significantly greater in size
than those observed in the base steel as pseudo-carburized at
1150
C. The reason is that abnormal grain growth in Nb
microalloyed steel was enhanced while the pseudo-carburizing
temperature was sufficiently high and the holding time was long
enough.
Adv. Eng. Mater. 2019, 21, 1900132
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The basic principle of precipitates suppressing austenite grain
coarsening at high temperature in steels was quantitatively
analyzed by Zener.[27] According to the equilibrium relationship
between the driving force of grain growth and the pinning force
of precipitates, the behaviors of grain growth obey the following
equation[27]
d
D¼A ð1Þ
f
where D is the grain size, A is the ratio of the radii of coarse and
matrix grains, d is the precipitate size, and f is the volume
fraction of precipitates. Zener first proposed that A was 4/3, but a
large number of experimental results later showed that the
driving force of grain growth was overestimated. Hillert’s theory
pointed out that pinning of grain boundaries would occur at two
levels, the corresponding values of the ratio were 2/3 and 4/9,
respectively. Normal grain growth stops at a lower level, and
abnormal grain growth reaches to the higher level. Most grains
grew abnormally in Nb microalloyed steel under the pseudo-
carburizing at 1150
C over 1 h along with at 1100
C over 8 h.
Therefore, the occurence of abnormal grain growth in Nb
microalloyed steel led to much larger mean grain size than
normal grain growth in the base steel. Hence, it is necessary to
strictly avoid abnormal grain growth in steels to obtain fine and
uniform grain structures. The carburizing of Nb microalloyed
steel is not suitable at temperatures higher than 1000
C for a
long time.
Obviously, the effect of pseudo-carburizing temperature on
austenite grain coarsening is more significant than holding
time. Abnormal grain growth in microalloyed steels can lead to
coarser austenite grain than those in plain carbon steels under
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identical heat treatment conditions. Nevetheless, the difference
in austenite grain coarsening behavior is mainly due to effects of
the microalloying and pseudo-carburizing conditions on
precipitate distribution characteristics, as described below.
3.3. Precipitates Behavior During Pseudo-Carburizing
Process
Austenite grain growth was significantly affected by precipitates
behavior in microalloyed steels. Four pseudo-carburized speci-
mens, selected based on specific differences in grain growth,
were examined in the TEM. Figure 5 shows the TEM images and
EDS spectram of typical precipitates in Nb microalloyed steel
pseudo-carburized at 1000
C and Nb–Ti microalloyed steel
pseudo-carburized at 1050, 1100, and 1150
C for 1 h, respec-
tively. Figure 6 shows the size distributions of precipitates
corrensponding to Figure 5. The average sizes of precipitates are
summarized in Table 2.
The precipitates revealed three primary morphologies:
spherical, cuboidal, and mixed morphology (Figure 5). Fine
and uniform precipitates observed in Nb-microalloyed steel
pseudo-carburized at 1000
C were identified as NbC, as shown
in Figure 5(a). Whereas precipitates observed in Nb–Ti
microalloyed steel pseudo-carburized at 1050–1150
C were
identified as (Nb, Ti)C, as shown in Figure 5(b–d). The fine NbC
and/or (Nb, Ti)C precipitates provided great pinning forces on
grain boundaries to inhibit grain growth. The increasing
temperature increased the solubility and coarsening rate of the
precipitates, and consequently reduced its stability. The average
size of (Nb, Ti)C precipitates in Nb–Ti microalloyed steel
pseudo-carburized at 1150
C for 1 h was the largest compared
to the steels pseudo-carburized at 1050 and 1100
C. EDS
analysis for the precipitates in Nb–Ti microalloyed steel
pseudo-carburized at 1050 and 1100
C for 1 h indicated that
it was Nb-rich with a small fraction of Ti. However, EDS
analysis for the precipitates in Nb–Ti microalloyed steel
pseudo-carburized at 1150
C for 1 h indicated that it was Ti-
rich with a small fraction of Nb. As the temperature increased,
the fraction of Nb decreased.
TEM observations show a few fine NbC precipitates in the Nb-
microalloyed steel as it was pseudo-carburized at 1000
C for 1 h.
The NbC precipitates started to dissolve at 1050
C, which was
consitent with the observed abnormal grain growth in Nb
microalloyed steel pseudo-carburized at 1050
C for 1 h (Figure 2
(f)). However, the volume fraction of the available effective (Nb,
Ti)C precipitates was sufficient to retard austenite grain
boundaries in the Nb–Ti microalloyed steel pseudo-carburized
at 1050
C for 1 h (Figure 2(i))). The austenite grains size of the
Nb–Ti microalloyed steel pseudo-carburized at 1100
C changed
sligtly (Figure 2(j) and (k)). The reason is that the (Nb, Ti)C
precipitates had dissolved and/or coarsed in some extent but not
exceed a critical size during pseudo-carburized at 1050–1100
C
held for 1 h. The abnormal grain growth was accelerated by
decreasing the volume fraction and increasing sizes of pinning
precipitates, resulting in unpinning of some grain boundary
regions. Such circumstances could be clearly seen in the Nb–Ti
microalloyed steel pseudo-carburized at 1150
C for 1 h (Figure 2
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(l)). This may be attributed to the rapid coarsening and
dissolution of the (Nb, Ti)C precipitates.
Figure 6 reveals that the relative fraction of coarse precipitates
increased with the temperatures. When pseudo-carburizing was
performed at 1150
C for 1 h, precipitates consisting of (Nb, Ti)C
in Nb–Ti steel exhibited a bimodal size distribution. Driving
force of grain growth significantly accelerated the non-uniform
grain growth, leading to the heterogeneity of precipitates size
distribution. On the other hand, the average size of precipitates
in Figure 6(d) was larger than the critical size (46.7 nm)
calculated by Gladman’s model,[28] which suggested that
abnormal grain growth takes place as follows
 
6Rm f 3 2 1
r crit ¼  ð2Þ
π 2 Z
where rcrit is the critical precipitate size at which abnormal grain
growth occurs, Rm is a grain size of matrix, and Z is the ratio of
the radii of coarse and matrix grains. Accoding to Equation (2),
most precipitates could not provide the pinning force to inhibit
the migration of grain boundaries. Thus, it is reasonable that the
abnormal grain growth was observed in Nb–Ti microalloyed
steel pseudo-carburized at 1150
C for 1 h (Figure 2(l)).
Compared with the Nb–Ti microalloyed steel, the absence of
fine and uniform austenite grain structures after pseudo-
carburizing at the relatively higher temperatures confirms that
the Nb microalloyed steel exhibited an insufficient number of
effective precipitates. As described above, the volume fraction of
precipitates in Nb–Ti microalloyed steel is higher than that of the
Nb microalloyed steel at the same austenitizing temperatures.
Another mechanism may contribute to the reduction in
austenite grain growth of the Nb–Ti microalloyed steel during
elevated temperatures is the reduction of the precipitate
coarsening rate due to Mo additions. Previous studies have
suggested that Mo additions have a distinct effect on the
precipitate size distribution evolution and associated austenite
grain refinement in Nb–Ti microalloyed steel.[29,30]
As pointed out by Speer and co-workers,[18] Mo may segregate to
the precipitate-matrix interface and reduce precipitate coarsening
rates, either by reducing the precipitate-matrix surface energy or by
reducing the precipitate-matrix interface mobility through solute
drag. Replacement of the Ti sub-lattice sites by Mo in ferrite results
in a reduction in interfacial energy and maintains better coherency
between precipitates and the ferrite matrix. A similar hypothesis
may be put forward for the incorporation of Mo in Nb–Ti
precipitates in austenite. The effect of Mo incorporation into the
Nb–Ti precipitates could produce a pronounced decrease in
precipitate-matrix surface energy and associated precipitate
coarsening rate in austenite through the mechanism of precipitate
reversion. On the other hand, the lower interfacial energy between
precipitates and matrix can reduce the nucleation energy barrier,
leading to a smaller critical nucleation radius. The effect of
reducing the critical nucleation radius by Mo in the Nb–Ti
precipitates in the early precipitation stage can result in
precipitates of a comparably tiny size. Therefore, additions of
Nb and Ti, are both beneficial in suppressing austenite grain
coarsening and delaying the onset of abnormal grain growth in the
18CrNiMo7-6 steel.
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Figure 5. TEM micrographs and EDS spectra of precipitates in microalloyed steels after different pseudo-carburizing treatments (a, b) Nb microalloyed steel,
1 h at 1000
C (c, d) Nb–Ti microalloyed steel, 1 h at 1050
C (e, f) Nb–Ti microalloyed steel, 1 h at 1100
C (g, h) Nb–Ti microalloyed steel, 1 h at 1150
C.

3.4. Kinetics of Austenite Grain Growth model, grain growth behaviors obey the following equation[31–33]
 
From the perspective of thermodynamics and kinetics, austenite grain Q
D ¼ At  exp 
n
ð3Þ
growth is a heat-activated migration process. The kinetics of grain RT
growth have been intensively studied. According to the Arrhenius

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Figure 6. Size distributions of precipitates in (a) Nb microalloyed steel, 1 h at 1000
C (b) Nb–Ti microalloyed steel, 1 h at 1050
C (c) Nb–Ti
microalloyed steel, 1 h at 1100
C (d) Nb–Ti microalloyed steel, 1 h at 1150
C.
where D is the average grain size, mm; A is constant that depends
on material; n is grain growth exponent, t is the holding time, s;
Q is the grain growth activation energy, J mol1; R is gas contant,
8.314 J mol1 K1; and T is the heating temperature, K.
Plots of lnD as a function of 1/T and lnt for the three steels are
shown in Figure 7 and 8. The plots of lnD via 1/T presented a
linear relationship. The Q values of base steel, Nb microalloyed
steel and Nb–Ti microalloyed steel were 34 630, 37450, and 65
960 J mol1, respectively. The change of Q value was due to the
presence of microalloying precipitates. An addition of Ti to the
Nb microalloyed steel, even in levels as low as 0.02 wt.%, yielded
significant differences in austenite grain coarsening behavior.
Nb–Ti microalloyed steel had the highest Q value, further
clarifying its strongest ability to suppress grain coarsening.
According to the calculation, the different grain growth models
can be obtained. In 850–960
C, growth kinetic model of the base
steel is D ¼ 258  t0.238  exp(34630/RT); in 850–1050
C,
growth kinetic model of Nb microalloyed steel is
D ¼ 323  t0.148  exp(37450/RT); in 1000–1150
C, growth
Table 2. Average size of precipitates after different pseudo-carburizing
treatments.
Pseudo-carburizing
Steel T/
C t/h Average precipitate size/nm
No. 2 1000 1 10
No. 3 1050 1 12
No. 3 1100 1 42
No. 3 1150 1 46
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kinetic model of Nb–Ti microalloyed steel is
D ¼ 5618  t0.078  exp(65960/RT). Therefore, microalloying
additions can significantly change the grain growth mechanism
of the base steel. Nb–Ti microalloying can be used to evaluate the
grain coarsening temperature of gear steels for high temperature
carburizing.
4. Conclusion
By investigating the effects of Nb–Ti microalloying on the
austenite grain coarsening of 18CrNiMo7-6 steel, the following
conclusions can be drawn:
1) As the pseudo-carburizing time is 1 h, grain coarsening
temperatures of the base steel, Nb microalloyed steel and
Nb–Ti microalloyed steel are 960, 1050, and 1150
C,
respectively. The effect of Nb–Ti microalloying on
increasing the grain coarsening temperature and inhibit-
ing the abnormal grain growth during high temperature
carburizing is much more significant than that of Nb
microalloying.
2) Abnormal grain growth in Nb microalloyed steel can lead to
coarser austenite grain structures than those in plain carbon
steel under identical heat treatment conditions. Nb micro-
alloying can not be successfully employed to design gear
steels for high temperature carburizing (>1000
C).
3) Compared to the base steel and Nb microalloyed steel,
simultaneous control of Nb, Ti, and N additions to precipitate
Nb and Ti as (Nb, Ti)C in Nb–Ti microalloyed steel provides
optimal resistance to grain growth at higher carburizing
temperatures, e.g., up to 1150
C.
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www.advancedsciencenews.com
Figure 7. Plots of lnD as a function of 1/T for the three steels (a) the base steel, (b) Nb microalloyed steel, (c) Nb–Ti microalloyed steel.
Figure 8. Plots of lnD as a function of lnt for the three steels (a) the base steel, (b) Nb microalloyed steel, (c) Nb–Ti microalloyed steel.
4) Grain growth models of the base steel and Nb–Ti micro-
alloyed steel are D ¼ 258  t0.238  exp(34630/RT) and
D ¼ 5618  t0.078  exp(65960/RT). Nb–Ti microalloying
has a significant influence on the grain growth kinetic of
the base steel and increases the grain growth activation
energy from 34630 to 65960 J mol1. Nb–Ti microalloying
provide the best potential for the development of gear steels
for high temperature carburizing (>1000
C).
Acknowledgment
The authors gratefully acknowledge support from the National Key
Research and Development Program of China (2016 YFB 0300603).
Conflict of Interest
The authors declare no conflict of interest.
Keywords
abnormal grain growth, grain growth kinetics, high temperature
carburizing, Nb–Ti microalloying, pinning effect of (Nb, Ti)C
Adv. Eng. Mater. 2019, 21, 1900132
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Received: February 2, 2019
Revised: April 12, 2019
Published online: June 11, 2019
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