International Journal of Offshore and Polar Engineering

Vol. 14, No. 2, June 2004 (ISSN 1053-5381)

Copyright by The International Society of Offshore and Polar Engineers
Effects of Cooling Rate and Isothermal Holding on Precipitation Behavior
During Solidication of Nb-Ti Bearing HSLA Steels
Hyun Jo Jun and C. G. Park
Department of Materials Science and Engineering, Pohang University of Science and Technology
Pohang, Korea
K. B. Kang
Technical Research Laboratories, POSCO, Pohang, Korea
ABSTRACT
The effects of the cooling rate and isothermal holding on precipitation behavior during solidication have been investigated
in 0.063C-0.017Ti-0.056Nb HSLA steels. The precipitates identied in an as-cast slab were semidendritic, dendritic or rod-
like Nb-rich (Nb,Ti)(C,N). The morphology and chemistry were quite different when these precipitates formed after reheating
and/or hot-rolling processes. No precipitation has been observed at the end of the solidication and the continuous cooling
down to 800C. ICP and TEM analyses indicated that most of the Nb and Ti was mainly precipitated into carbonitrides by
the isothermal holding at a temperature range of 900 to 1000C. In the case of a continuous casting process, the isothermal
holding region corresponds to a certain at cooling region, probably due to the latent heat of solidication. The Nb-rich
carbonitrides formed during solidication are associated with the microsegregation of Ti and Nb in the interdendritic
region.
INTRODUCTION
Micro-alloying elements in steels, such as Ti, Nb and V, can
facilitate grain renement through precipitation in austenite, and
contribute to dispersion hardening through precipitation in fer-
rite during or after o transformation. Especially, titanium
has frequently been added to high-strength, low-alloy (HSLA)
steels to enhance the control of austenite during the welding
or reheating process. In addition, TiN precipitates of a suitable
size can suppress austenite grain coarsening in subsequent high-
temperature processes such as welding or reheating, thus improv-
ing the toughness of nal steel products (Cuddy, 1983). Multi-
micro-alloying, then, can lead to the formation of complex com-
pounds, which can inuence the mechanical properties of the
HSLA steels.
Very large precipitates could also be found in Nb-Ti HSLA
steels produced by a continuous casting process (Chen, 1987;
Zhou, 1996). It is, however, unlikely that these large precipi-
tates can play any useful role in rening grain size. Instead,
their harmful effects on the distribution and formation of smaller
precipitates can weaken the role of Nb and Ti as grain reners
during the subsequent reheating and hot rolling processes (Hong,
2003).
The objectives of the present study are both to identify the
precipitates formed in a continuously cast slab, and to examine the
effects of post-solidication cooling on the precipitation behavior
in Nb-Ti bearing HSLA steels.
Received August 18, 2003; revised manuscript received by the editors
February 9, 2004. The original version (prior to the nal revised
manuscript) was presented at the ISOPE Symposium on High-Per-
formance Materials in Offshore Industry, the 13th International Off-
shore and Polar Engineering Conference (ISOPE-2003), Honolulu,
Hawaii, USA, May 2530, 2003.
KEY WORDS: Precipitate, carbonitride, solidication, cooling rate, iso-
thermal holding.
EXPERIMENTALS
Materials
Table 1 gives the chemical composition of the investigated slab.
POSCO (Pohang Iron & Steel Co. Ltd.) produced the slab of Nb-
Ti bearing HSLA steel.
Simulation for Solidication and Cooling
Simulation of the solidication and cooling was conducted using
the Gleeble 3500 system (Dynamic System Inc.). Rod samples
120 mm in length and 10 mm in diameter were machined from
the 1/4 and 3/4 positions of the slab thickness. The quartz tube
was used for shielding the sample during the melting and solid-
ication processes. The samples welded with an R-type thermo-
couple were heated from room temperature to melting temperature
(14701480C). In order to fully dissolve Nb and Ti in steels,
the melt was held for 3 min and cooled down as follows, as shown
in Fig. 1: (1) Cooling to 800C at various cooling rates (10, 100,
200, 300C/min) followed by water quenching in order to iden-
tify the effect of the cooling rate on precipitation, and (2) cooling
to various holding temperatures from 700 to 1200C at the cool-
ing rate of 100C/min, followed by isothermal holding for 30 min
in order to evaluate the precipitate-forming temperature.
Quantitative Analysis and TEM Observations of Precipitates
The quantitative amount of Nb and Ti precipitated was mea-
sured using inductively-coupled plasma (ICP) spectroscopy. At
rst, a few grams of samples were electro-chemically dis-
solved, and then ltered with a polycarbonate membrane l-
C Si Mn Nb Ti N
Slab 0.063 0.2 1.58 0.056 0.017 0.006
Table 1 Chemical composition of investigated slab (wt.%)
International Journal of Offshore and Polar Engineering, Vol. 14, No. 2, June 2004 133
Fig. 1 Thermal schedules of simulation for solidication and
cooling: (a) continuous cooling, and (b) isothermal holding
ter. The ltered precipitates were melted in a buffer solution
(Na
2
CO
3
: H
3
BO
3
= 3 : 1) and mixed with 10% HCl solution to
perform the ICP analysis.
The morphology, distribution and chemical composition of the
precipitates were examined using TEM-extracted replicas. The
replica lm (carbon or aluminum) was deposited on the sur-
face of the sample to extract precipitates from various sample
surfaces after mechanical polishing and electro-chemical etch-
ing. The replicas released by electro-polishing were then exam-
ined using FEG-TEM (JEM-2010F) equipped with ATW-EDS
(Oxford Inc.)
RESULTS
Precipitates Formed in Cast Slab
The morphology of the precipitates formed in a continuously
cast slab was quite complex. Fig. 2 shows 3 different types of typ-
ical precipitates: semidendritic (a), dendritic (b), and rod-like (c).
The chemistry of these precipitates was investigated using nano-
beam EDS analysis. All precipitates were identied as complex
carbonitrides mixed with Nb and Ti (Fig. 2d and e).
Most of the precipitates formed in the slab were revealed as
semidendritic; these were quite small, ranging from 50 to 200 nm.
Large dendritic precipitates varied from 0.5 to 1 jm were rarely
observed. Rod-like precipitates with a length of up to a few jm
were usually formed along austenite grain boundaries. An impor-
tant fact is that these dendritic carbonitrides are not Ti-rich, but
Nb-rich. The fraction of Ti in these precipitates, Ti/(Ti+Nb), was
approximately 0.3.
The morphology and chemistry of the precipitates formed in
the cast slab were quite different from those of the precipitates
formed after reheating and/or hot rolling. It has been well reported
that the precipitates of Nb-Ti HSLA steels are identied as large
cuboidal TiN formed after the reheating process, as shown in
Fig. 3a (Hong, 2003). Plus, the strain-induced NbC carbides usu-
ally found in hot-rolled steels are additionally nucleated heteroge-
neously at the pre-exited TiN, as shown in Fig. 3b (Hong, 2002).
Thus, the present results imply that the precipitates found in cast
slabs are quite different.
Effects of Cooling Rate on Precipitation
It is generally well known that the dendritic shape is a typi-
cal morphology of solidication (liquid solid transformation),
which is dependent on the cooling rate. It is then suggested that
precipitation starts simultaneously during the solidication from
liquid to solid, and that precipitation is also dependent on the
cooling rate. Thus, simulation for solidication and cooling were
performed down to 800C at different cooling rates (10, 100,
200, and 300C/min).
(a)
(b)
(c)
(d)
(e)
100nm
100nm
200nm
Ti/(Ti+Nb) ~ 0.3
Fig. 2 Al replicas showing morphology of precipitates in slab:
(a) semidendritic, (b) dendritic, (c) rod-like and (d)(e) EDS spec-
tra of (b) and (c), respectively (Al and Cu peaks generated from
Al lm and Cu grid)
At rst, the carbon replica of the sample quenched at the end
of solidication did not reveal any precipitate, which conrmed
the complete dissolution of Nb and Ti.
The amounts of Nb and Ti precipitated in the cast slab and the
simulated samples were measured by the ICP method (Fig. 4).
In the cast slab, both Nb and Ti were fully precipitated into car-
134 Effects of Cooling Rate and Isothermal Holding on Precipitation Behavior During Solidication of Nb-Ti Bearing HSLA Steels
(a)
(b)
(c)
200nm
A : (Nb,Ti)C
B : (Ti,Nb)(N,C)
Fig. 3 TEM micrographs showing typical morphology of precipi-
tates formed after (a) reheating and (b) hot-rolling processes, and
(c) EDS spectra of precipitate shown in (b) (Hong, 2002, 2003)
bide or nitride (Fig. 4A). In the simulated samples, however, the
amounts of both Nb and Ti were signicantly lower than those in
the cast slab (Fig. 4B). The fraction of Nb and Ti contained in the
precipitates of the simulated samples was evaluated as 5% to 10%
and 10% to 30%, respectively, of total additions. The amounts
gradually decreased with an increasing cooling rate, because of
insufcient diffusion time with the increase of the cooling rate.
The low levels of the precipitated amounts in the simulated sam-
ples suggest that the solidication and the following continuous
cooling (down to 800C) are not the major precipitation region.
In order to evaluate the morphology and chemistry of the pre-
cipitates depending on cooling rates, carbon replicas of the 2 sam-
ples at the cooling rate of 10 and 300C/min were observed using
FEG-TEM with nano-beam EDS. The precipitates were rarely
slab 10C/m 100C/m 200C/m 300C/m
0.00
0.01
0.02
0.03
0.04
0.05
0.06
B A
Total Ti addition
Total Nb addition
A
m
o
u
n
t

(
w
t
.
%
)
Cooling rate
Nb
Ti
Fig. 4 Amounts of Nb and Ti precipitated in precipitates formed
in cast slab, and in simulated samples measured by dissolution
and ltration
observed, compared to those of the cast slab. The morphology
of most precipitates in the simulated samples was identied as
semidendritic (Fig. 5). The size of the precipitates observed in
the sample with slow cooling rate (10C/min) varied from 50 to
150 nm, which was larger than that of the precipitates (below
50 nm) in the sample with fast cooling rate (300C/min). The
chemistry of the precipitates observed in the 2 samples was iden-
tied as Nb-rich (Nb,Ti)(N,C), which was similar to that of the
precipitates found in the cast slab. However, the atomic fraction of
Ti, Ti/(Ti+Nb) was different between the 2 samples: about 1/3 in
the slow-cooled sample and about 1/4 in the fast-cooled sample.
These results imply that the amount of Nb and Ti in the precipi-
tates decreases with an increasing cooling rate, which is in good
agreement with the previous results obtained from ICP analysis.
Precipitate Forming Temperature During Solidication
In order to evaluate which temperature region is an effec-
tive region for precipitation during solidication and cooling,
isothermal holding experiments were performed using the Glee-
ble 3500 system. The precipitates were examined in the simulated
samples, which were isothermally held at various temperatures
(7001200C) for 30 min.
Fig. 6 shows the amount of Nb and Ti contained in the pre-
cipitates measured by the ICP method. Most of the Nb and Ti
was precipitated in the samples held at the temperature region
of 9001000C. In the samples held at 700 and 800C, the
amounts were approximately 50% of the total additions. No pre-
cipitate was observed in the sample held at 1200C.
TEM observation of the precipitates also revealed results similar
to those measured by the ICP analysis. The precipitates of the sam-
ple held at 800C in Fig. 7 showed quite a small (below 50 nm in
size) and irregular dendritic shape because of low diffusivity in low
temperatures. The precipitates of the sample held at 1000C had 3
morphologies: semidendritic (a), dendritic (b) and rod-like (c), as
shown in Fig. 8. These results are in good agreement with those
of the precipitates formed in the cast slab (Fig. 2).
The chemistry of precipitates, as shown in Fig. 8(d) was similar
to that of the cast slab. No precipitate could be observed in the
sample held at 1200C. These results indicate that the isothermal
holding at 9001000C during solidication and cooling is the
major precipitation region of Nb and Ti.
International Journal of Offshore and Polar Engineering, Vol. 14, No. 2, June 2004 135
(a)
(b)
10 C/min
300 C/min
Ti/(Ti+Nb)~0.33
Ti/(Ti+Nb)~0.24
Fig. 5 TEM micrographs and EDS spectra of samples cooled at
rate of (a) 10C/min, and (b) 300C/min
700 800 900 1000 1100 1200
0.00
0.01
0.02
0.03
0.04
0.05
0.06
Total Ti addition
Total Nb addition
CR=100
0
C/min
Holding time: 30 min
A
m
o
u
n
t

(
w
t
.
%
)
Holding temperature (C)
Nb
Ti
Fig. 6 Amounts of Nb and Ti in precipitates depending on hold-
ing temperatures
80nm
(a) (b)
Fig. 7 TEM micrographs showing precipitates in simulated sam-
ple held at 800C for 30 min
DISCUSSIONS
ICP and TEM analyses on the precipitates indicated that most
of the Nb and Ti were precipitated into carbonitrides by isother-
mal holding from 900 to 1000C. In case of a continuous
casting process, the isothermal holding region corresponds to a
(a)
(b)
(c)
(d)
Ti/(Ti+Nb)~0.3
Fig. 8 TEM micrographs showing precipitates and EDS spectrum
holding at 1000C for 30 min
136 Effects of Cooling Rate and Isothermal Holding on Precipitation Behavior During Solidication of Nb-Ti Bearing HSLA Steels
Fig. 9 Thermal history of continuous casting process (Subrama-
nian, 1985)
certain very slow cooling region, probably due to the latent heat
of solidication. The thermal history measured during the contin-
uous casting process showed the at cooling region to be similar
to the isothermal holding region at 10501150C (Subramanian,
1985), as shown in Fig. 9. The temperature of this at region is
somewhat higher than that of the simulation results, which seems
to be caused by the latent heat of solidication.
Nano-beam EDS results reveal that the precipitates observed
in both the cast slab and the simulated samples are not Ti-rich,
but Nb-rich. If these precipitates are formed at the end of solidi-
cation around 1400C, they should be the Ti-rich carbonitrides,
as predicted by the regular solution model (Houghton, 1982).
Houghton also proposed that TiN particles are precipitated rst
in the liquid and at high temperatures above 1300C in austenite,
followed by the precipitation of Nb and Ti carbonitrides as the
temperature decreases. No precipitate, however, was observed in
the high-temperature region in the present study. Although embryo
may form in the high-temperature region of austenite, the present
results reveal that most of the Ti and Nb is precipitated in the
supersaturated austenite at around 1000C. This is in good agree-
ment with the equilibrium composition at around 1000C calcu-
lated by Thermo-calc, TCFE2000 (Fig. 10).
Nb-rich dendritic carbonitrides are not observed after the
reheating and hot-rolling processes, as already mentioned by
Hong (2002, 2003). The Nb-rich dendrite carbonitrides observed
600 800 1000 1200 1400 1600
0.00
0.01
0.02
0.03
0.04
0.05
0.06
0.07
Composition
range observed by EDS
A
m
o
u
n
t

(
w
t
.
%
)
Temp. (
0
C)
Nb
Ti
Fig. 10 Equilibrium composition of complex carbonitride calcu-
latd by Thermo-Calc, TCFE2000
in the present study may be attributed to the microsegregation
of Nb and Ti in the interdendritic liquid, since these were only
formed during solidication. Assuming no diffusion in the solid
and complete mixing in the liquid (Flemings, 1974), the local seg-
regation can be calculated as:
C
L
,C
0
=]
(k1)
L
(1)
where C
L
and C
0
are liquid and initial composition, respectively,
]
L
is liquid fraction, and k is the equilibrium distribution coef-
cient. The k values of Nb and Ti are 0.3 and 0.61, respectively
(Elliott, 1965). The segregation ratios C
L
,C
0
for Nb and Ti in
5% liquid fraction are 8 and 3, respectively. This calculation indi-
cates that the stronger segregation ratio of Nb may be responsi-
ble for the formation of Nb-rich dendritic carbonitrides. Although
the interdendritic liquid homogenizes partially during solidica-
tion and cooling, the locally supersaturated austenite may remain
because of the absence of precipitation during the solidication
and cooling. Zhou (1996) also reported that MnS and TiN formed
in liquid could catalyze the formation of complex carbonitrides
during the solidication and cooling. However, there was no for-
mation of MnS and TiN in the present study.
It is believed that the dendritic carbonitrides formed in an
as-cast slab can affect the size and distribution of the precipi-
tates formed during the following reheating and hot-rolling pro-
cesses. From the previous results (Hong, 2003), it is predicted that
the Nb-rich dendritic carbonitrides will dissolve, and then repre-
cipitate to 2 kinds of carbonitridescuboidal TiN and Ti-rich
(Ti,Nb)(N,C)during the reheating process because of the ther-
mal instability of Nb-rich carbonitrides. These reprecipitated car-
bonitrides can play important roles in the precipitation kinetics of
NbC, as heterogeneous nucleation sites during hot rolling (Hong,
2002; Jun, 2003). Detailed discussion of the relationship between
the precipitates of an as-cast slab and those of reheating and hot-
rolling samples will be found elsewhere (Jun, 2003).
CONCLUSIONS
The simulation for solidication and cooling was performed in
Nb-Ti bearing HSLA steel. The morphology and microchemistry
of the precipitates observed in a continuously cast slab and simu-
lated samples were investigated by TEM observation with nano-
beam EDS. The main results are:
The precipitates in a continuously cast slab show 3 different
morphologies, semidendritic, dendritic and rod-like. The chem-
istry of these precipitates is Nb-rich, which is thermodynamically
stable at temperatures lower than 1000C.
The amounts of Nb and Ti in the precipitates are almost inde-
pendent of the cooling rate during solidication. ICP and TEM
analyses indicate that most Nb and Ti is mainly precipitated into
carbonitrides by the isothermal holding at a temperature range of
900 to 1000C.
In case of a continuous casting process, the isothermal hold-
ing region corresponds to a certain at cooling region, probably
due to the latent heat of solidication.
The Nb-rich carbonitrides formed during solidication are
associated with the microsegregation of Ti and Nb in the inter-
dendritic region.
ACKNOWLEDGEMENTS
The authors would like to thank POSCO (Pohang Iron & Steel
Co. Ltd.) for technical and nancial support.
International Journal of Offshore and Polar Engineering, Vol. 14, No. 2, June 2004 137
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