AIST Transactions

Vol. 11, No. 4

Cooling Rate Effects on the As-Cast Titanium

Nitride Precipitation Size Distribution in a
Low-Carbon Steel
The present work was undertaken
to examine effects of cooling
rate on the titanium nitride
precipitation size distribution in
one alloy over a more extensive
range of post-solidification
cooling rates. The titanium nitride
precipitation in thick slab, thin
slab and thin strip material was
simulated using a commercially
produced 0.04C, 1.23Mn steel
with near-stoichiometric titanium
and nitrogen levels.

Authors

J. Stock (top row, left) (stock.

julian@gmail.com), The
George S. Ansell Department
of Metallurgical and Materials
Engineering, Colorado School
of Mines, Golden, Colo., USA;
C.M. Enloe (not pictured)
(charles.enloe@severstalna.
com), Severstal North America,
Dearborn, Mich., USA; R.J. OMalley (top row,
center), F. Kenneth Iverson Chair Professor, and
director, Kent D. Peaslee Steel Manufacturing
Research Center (omalleyr@mst.edu), Missouri
University of Science & Technology, Rolla, Mo.,
USA; K.O. Findley (top row, right), assistant
professor (kfindley@mines.edu), The George S.
Ansell Department of Metallurgical and Materials
Engineering, Advanced Steel Processing and
Products Research Center, Colorado School
of Mines, Golden, Colo., USA; and J.G. Speer
(bottom), John Henry Moore Distinguished
Professor of Metallurgical and Materials
Engineering, The George S. Ansell Department
of Metallurgical and Materials Engineering, and
director, Advanced Steel Processing and Products
Research Center (jspeer@mines.edu), Colorado
School of Mines, Golden, Colo., USA

180 Iron & Steel Technology

ith high yield strength,

toughness and good weldability, microalloyed steels are
widely used in the automotive,
pipeline and transportation
industries. An understanding of
the thermodynamics and kinetics of microalloy precipitation
during casting and cooling can
be important to microstructure
control. Titanium nitride (TiN)
precipitation is considered here,
as TiN has high stability and
may precipitate at temperatures
near the liquidus. TiN precipitates may remain stable at elevated temperatures during later
processing, suppressing grain
growth during solid-state processing or in weld heat-affected
zones. Smaller precipitates have
a greater effect on the grain
boundary pinning, and therefore the TiN size distribution is
important.
Sage and Cochrane previously evaluated the relationship
between cooling rate and TiN
precipitate size. An inverse linear relationship between particle size and logarithmic cooling
rate during/after solidification
was reported.1 The scope of the
present study was to examine
TiN formation during casting
over an expanded range of cooling rates applicable to newer
processes.

Background
Previous research by Sage and
Cochrane1 examined vanadiumand titanium-containing steels
for welding applications in the
offshore and construction industries. Both vanadium nitrides
(VN) and titanium nitrides
(TiN) contributed to the production of a fine grain size.1
Since titanium nitrides have the
ability to control the austenite
grain size during the welding
process, these particles have an
important role of maintaining
toughness in the heat-affected
zone. TiN precipitates form in
the liquid during casting, so
Sage and Cochrane investigated
different sized ingots and different locations within these
solidified ingots, associated with
different post-solidification cooling rates. For their cooling rate
study, three trial heats were used,
as shown in Table 1.
The temperature at each location during and after solidification was monitored, and the cooling rate was determined. Particle
sizes were determined with a
transmission electron microscope (TEM) on extraction replicas. Results from that study are
summarized in Figure1.
It was found that the particle
size decreases with increasing
cooling rate, and it was suggested that this relationship could be

A Publication of the Association for Iron & Steel Technology

Table 1
Chemical Composition of Experimental Steels Used by Sage and Cochrane1 (in wt. %)
Steel

Mn

Si

Ti

Al

N [ppm]

0.14

1.65

0.44

0.006

0.052

0.026

120

0.011

0.017

0.12

1.56

0.25

0.012

0.039

0.027

80

0.009

0.017

0.12

1.60

0.38

0.013

0.047

0.030

80

0.009

0.016

Figure 1

Experimental Procedure
For this study, a low-carbon steel with the chemical
composition shown in Table 2 was used, as reported
by the manufacturer. This commercially thin-slab
cast material was provided by Nucor SteelArkansas,
Hickman, Ark., USA, and has near-stoichiometric titanium and nitrogen levels. The material was machined
into 10-mm-thick and 121.5-mm-long specimens
for melting and casting simulation.2 A thread was
machined on each end, to be able to strain the
sample while heating it. For the casting simulations a
Gleeble 3500 simulator was employed with a pocket
jaw mobile conversion unit using solid water-cooled
copper 10-mm round bar grips, which provide efficient heating and cooling.
For temperature monitoring, an R-type thermocouple was welded at the mid-length of the specimen.
To contain the molten steel, a quartz tube, 31 mm
in length and 10.2 mm internal diameter, was slid
over the sample. To prevent oxidation while melting
the sample, the Gleeble chamber was evacuated and
flushed with argon twice before heating in an argon
atmosphere at a pressure 225 Torr below atmospheric.
The complete setup can be seen in Figure 2.

120

Titanium Nitride Particle Size [nm]

represented by the negative log-linear trend shown in

Figure 1. Sage and Cochrane stated that, in the higher
cooling rate conditions, no large particles were found.
For the cooling rate conditions of 8, 14 and 16C/
minute, however, it was indicated that some particles
larger than 1 m were found.1 The error bars in the
plot were included to represent the upper and lower
limits of the particle size ranges, excluding the largest
particles assumed to precipitate in the interdendritic
liquid.

100
80
60
40
20
0

10

30

20

40

50

Post-Solidification Cooling Rate [K/min]

Titanium nitride (TiN) particle size as a function of the
post-solidification cooling rate (PSCR).1

Each sample was heated by electrical resistance to

1,526C until the central region (~10 mm in length)
of the sample was fully molten. The dwell time at
this temperature was short enough to avoid chemical
reactions with the quartz containment tube, but long
enough to enable pre-existing TiN to fully dissolve.
Each sample was heated to 1,450C within 30 seconds.
For safety reasons, the temperature was then manually
increased up to the melting temperature and held
at this temperature for approximately 10 seconds. A
schematic of the heating and cooling process can
be seen in Figure 3. At the melting temperature of
1,526C, all of the TiN should be in solution at equilibrium. It is believed that all of the TiN was dissolved

Table 2
Chemical Composition of the Experimental Steel (in wt. %)
C

Mn

Si

Cr

Mo

Ti

Al

Cu

0.046

1.23

0.012

0.045

0.013

0.022

0.005

0.022

0.007

0.003

0.006

0.090

AIST.org 

June 2014 181

Figure 2
Centerline cooling rate of a thick slab,
240mm: 0.1 K/second.4
Columnar region cooling rate of a thin slab,
50mm: 5.0 K/second.5
Near surface cooling rate of a thin strip:
600 K/second.

View into the Gleeble chamber. The standard pocket jaw

casting setup including water-cooled copper grips, casting specimen, quartz tube and R-type thermocouple can
be seen.

Figure 3
Heating
600 K/s
5 K/s
0.1 K/s

Temperature [C]

1400
1200

1600
1400

1000

1200

800

1000

600

800

400

600

200
0

1800

Temperature [K]

1600

400
0

75

150 225 4200 4800 5400 6000

Time [s]

Experimental thermal profiles. Specimens were melted by

heating to a temperature of 1,526C and then cooled at
one of the three cooling rates to 1,000C, followed by grip
quenching to room temperature.

during heating in the present study, consistent with

earlier work,3 and with the absence of any coarse TiN
particles in the specimens cooled rapidly from the
liquid.
Subsequent to the heating, the sample was cooled
to a temperature of 1,000C at one of the three cooling rates selected to represent a particular production
process and position within the casting. The cooling
rates were as follows:

182 Iron & Steel Technology

For the low (0.1 K/second) and medium (5 K/second) cooling rates, grip cooling was sufficient. For
the high cooling rate (600 K/second), however, rapid
cooling was achieved by spraying gaseous helium
onto the sample surface. Initially, a thin-strip surface
cooling rate of 1,700 K/second was planned.6 It was
found, using the Gleeble 3500 casting setup in this
temperature regime, that 600 K/second was the maximum achievable cooling rate. Once the specimen was
cooled to 1,000C, each sample was quenched by
shutting off the Gleebles heating power and then grip
cooling to room temperature. Schematic thermal profiles for the casting simulations are shown in Figure 3.
The quenching temperature of 1,000C was chosen
based on an analysis of the TiN solubility. Using the
solubility product expression in Equation1,7 less than
1 wt. % of titanium should remain in solution in austenite under equilibrium conditions at a temperature
of 1,000C.

log K TiN = log [%Ti][%N ] =

15, 790
+ 5.40
T
(Eq. 1)

where
KTiN is the solubility product of TiN,
[%Ti] and [%N] are the solute concentrations of Ti
and N in austenite, respectively in wt. % and
T is the temperature in Kelvin.
After processing, each specimen was cut into smaller
pieces. The central region, where the temperature was
recorded, was sectioned for metallography, mounted
in Bakelite, ground to 600 grit and polished down to
1 m using a diamond suspension. The samples were
lightly etched for 30 seconds using a 2% Nital solution and subsequently coated with a thin carbon film
for replication. Only the near-surface portion of the
cross-sectional area close to the thermocouple position was coated. Then each sample was etched in a 5%
Nital solution for a few minutes, to release the replicas,
which were captured on Cu grids. Specimens were
examined by TEM in brightfield using a FEI (Phillips)
CM 200. At least two different replicas were examined
for each condition. On each replica, at least three
grids were examined, and ImageJ software was used
to measure the TiN particle size. For each particle,
A Publication of the Association for Iron & Steel Technology

Figure 4
excess nitrogen was present, it was presumed that the
cuboidal precipitates are TiN.
At elevated temperatures, the possibility of reactions
between the atmosphere and melt was of concern.
Therefore, the formation of oxides was suppressed
by running the simulation in an argon atmosphere.
Reactions between the quartz tube and the melt at elevated temperatures were still possible, so the chemical
composition of a melted and resolidified sample was
compared to the composition of an untested casting
specimen, as shown in Table 3. It is noted that the
levels of C, Si and Ti were not substantially changed
after remelting. It was therefore concluded that any
reactions between the quartz tube and specimen are
not significant.
Example of the two-dimensional measurements taken
from a representative TiN particle.

two measurements were taken and averaged, as shown

using the example in Figure 4. For the cooling rates
of 0.1, 5 and 600 K/second, 120, 330 and 885 precipitates were measured, respectively. Most of those
precipitates were of cuboidal shape with some minor
variations. Some precipitates were found to show less
distinct edges. Due to the much greater stability of
TiN compared to TiC at the investigated range of temperature (liquidus 1,000C) and the fact that some

Results and Discussion

Figure 5 shows representative titanium nitrides found
in the three steels cooled at different rates during
and after solidification. All three micrographs were
recorded at the same magnification and therefore
show quite effectively the dramatic differences in TiN
particle size between the three different cooling rates
representing different industrial casting processes.
Clearly, the TiN particle size is diminished at faster
cooling rates, as expected, and consistent with the
general trend reported in prior work.1

Table 3
Composition for an Untested and Tested (Remelted and Solidified) Gleeble Casting Sample (in wt. %)
Material

Mn

Si

Ni

Cr

Mo

Ti

Nb

Al

Cu

Untested

0.048

1.28

0.024

0.030

0.040

0.016

0.025

0.002

<0.001

0.016

<0.001

<0.001

0.078

Tested

0.053

1.21

0.029

0.054

0.039

0.013

0.022

0.012

<0.001

0.016

<0.001

<0.001

0.089

Figure 5

(a) (b) (c)

Representative transmission electron microscopy micrographs of carbon extraction replicas for the 0.1 K/second (a),
5K/second (b) and 600 K/second (c) cooling rates. The inset in (c) shows the small precipitates at higher magnification.
AIST.org 

June 2014 183

Figure 6
Particle size distributions, which can be seen in
Figure 7, are suggestive of bimodal characteristics,
and the overlaid curves fitted to the data include a
log-normal distribution at small particle sizes and a
normal distribution for larger particles. In the case of
the 0.1K/second cooling condition, the particle sizes
range from 9to2,400nm. Approximately 90% of all
measured particles are found in the log-normal part,
whereas about 10% of the precipitates are larger than
1,000nm. Most of the particles, however, are smaller
than 250nm. It is believed that the large precipitates
may have formed in the interdendritic liquid, whereas
the small particles formed in the solid.10 The medium
cooling rate condition (5 K/second) exhibits smaller
particles compared to the 0.1K/second cooling rate.
The precipitate sizes range from 3 to 883 nm. The
bimodal character was again evident. With increasing cooling rate, not only did the overall particle
size decrease, but also the range of the distribution
decreased. For the high cooling rate condition (600
K/second), an even smaller range of particle sizes
was found. The largest precipitate measured was
58 nm and the smallest particles were around 3 nm.
Such fine TiN particles could contribute to precipitation strengthening, and suggest a potential new TiN
strengthening mechanism that might be applicable,
for example, to thin strip products.
In order to obtain an overall particle size value for
each of the three cooling conditions, average sizes
were calculated from the distributions that were fitted to the data. Average sizes for the fine and coarse
components of each distribution are presented in
Table 4. In Sage and Cochranes earlier study,1 the
larger particles were presumed to have formed in the
interdendritic liquid, and were excluded from their

TiN particles formed in the 600 K/second cooling condition; clustering of the particles was observed.

Overall, the precipitates appeared similar when

viewing different regions of the carbon extraction
replicas. While the precipitates in Figure 5 do not
necessarily represent the precise average particle
size for the specific cooling rate condition, they were
typical and represent the overall differences between
the three conditions. In the low cooling rate samples
(0.1 K/second, Figure 5a), larger TiN particles were
present. Several particles reached a size in the range
of 12.5 microns. Those particles were visible under
a conventional light optical microscope. In the case
of the high cooling rate samples (600 K/second,
Figure 5c), the much smaller particles were often
grouped in clusters of up to 30 precipitates. An example of fine particle clustering is shown in Figure 6. It is
believed that the clustering of small precipitates happened during, and is an artifact of, the preparation of
the replicas.9

Figure 7

Number of Particles

180
150
120
90
60

900

800

30

Particle Size [nm]

600 K/s Cooling Rate Condition

210

10
700

2400

2100

1800

1500

900

1200

600

300

20

600

11

30

500

17

40

400

23

50

300

29

60

35

100

Number of Particles

Number of Particles

41

Particle Size [nm]

5 K/s Cooling Rate Condition

70

200

0.1 K/s Cooling Rate Condition

47

5 10 15 20 25 30 35 40 45 50 55 60

Particle Size [nm]

(a) (b) (c)

TiN precipitate size distribution for the 0.1 (a), 5 (b) and 600 K/second (c) cooling conditions, including experimental data
and fitted curves. Note changes in scale of abscissa.
184 Iron & Steel Technology

A Publication of the Association for Iron & Steel Technology

Table 4
Mean Particle Size for Fine and Coarse TiN Distributions in Each Cooling Condition. The standard deviation and
fraction of particles in each component of the distribution are also shown.
Cooling
condition

Fit to fine
distribution

Standard
deviation

Fraction of
particles

Avg.
particle
size (nm)

Fit to
coarse
distribution

Standard
deviation

Fraction of
particles

Avg.
particle
size (nm)

0.1 K/second

Log-normal

1.21

0.92

101.0

Normal

0.11

0.08

1,897.0

5 K/second

Log-normal

1.49

0.84

22.5

Normal

0.22

0.16

537.0

600 K/second

Log-normal

0.27

0.89

6.7

Normal

0.30

0.11

22.8

Figure 8
Titanium Nitride Particle Size [nm]

analysis since those particles do

120
not contribute as effectively to
Current Study
grain size control as smaller parA.M. Sage,
100
R.C. Cochrane, 1988
ticles.8 To compare the results
of the current study to those of
80
Sage and Cochrane, the average
particle size from the log-normal
60
distribution was used to characterize each steel.
40
The average particle size is plotted in Figure 8 versus cooling
20
rate for the present work, along
0
with the prior results of Sage
10
100
1,000
10,000
100,000
3
and Cochrane.1 The overall trend
Post-Solidification Cooling Rate [C/min]
of decreasing particle size with
increasing cooling rate is illusTiN particle size as a function of the PSCR. The current data (green squares) as
trated. For low cooling rates, the
well as Sage and Cochranes data (open red diamonds) are included.
average particle size is quite comparable to results from Sage and
Cochrane. The medium (5 K/
second) and high (600 K/second)
cooling rate data expand the range of cooling rates
faster solidification may have interesting implications
beyond the earlier work, and show that the trend
for other compounds that can precipitate at high
becomes non-linear over the wider range of cooling
temperatures in austenite. For example, it may be posrates. As mentioned previously, the TiN distributions
sible to employ higher Nb additions, utilize MnS for
obtained at the high cooling rate may be of special
beneficial purposes, etc.
interest in the context of thin-strip casting.

Conclusions
The expected general trend of increasing particle
size with decreasing cooling rate was confirmed over
the range of cooling rates representing thick-slab
through thin-strip processing. The range of cooling
rates reported by Sage and Cochrane was successfully
expanded and now also gives valuable information for
future products subjected to accelerated cooling rates
during solidification, e.g., thin strip. The presence
of nanoscale titanium nitrides at high cooling rate
suggests that a new strengthening mechanism may be
available to enhance the properties of rapidly cooled
steels. The increased supersaturation associated with
AIST.org 

Acknowledgments
The authors gratefully acknowledge the support of
the sponsors of the Advanced Steel Processing and
Products Research Center, an industry/university
cooperative research center at the Colorado School
of Mines.

References
1. A.M. Sage and R.C. Cochrane, The Development of a
Weldable Normalized Vanadium Titanium Structural Steel,
Vanadium International Technical Committee (Vanitec),
London, November 1988.

June 2014 185

2. Gleeble 3500/3800 Technical Reference and Maintenance

Manual, DSI, 2007.
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6. P. Campbell, R. Wechsler, G. Gillen and N.S. Indiana, The
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7. E.T. Turkdogan, Cause and Effects of Nitride and Carbonitride

Precipitation During Continuous Casting, Iron & Steelmaker,
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8. M.A. Linaza, J.L. Romero, J.M. Rodriguez-Ibabe and J.J.
Urcola, Influence of the Microstructre on the Fracture
Toughness and Fracture Mechanisms of Forging Steels
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9. C.M. Enloe, The Effect of Molybdenum on Niobium, Titanium
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a Conference Held at the University of Sheffield, Sheffield
Hallam University, U.K., December 1994, p. 27.
F

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