Journal of Iron and Steel Research, International, 2014, 21 (Supplement 1)

Genetic Analysis for Large TiN Inclusions in Wire Rod for

Tire Cord Steel of SWRH82A
Yue-dong JIANG1,2, Zheng-liang XUE1, Jing ZHANG1
(1. The State Key Laboratory of Refractories and Metallurgy, Wuhan University of Science and Technology, Wuhan
430081, Hubei, China; 2. Research and Development Center of Wuhan Iron and Steel Group, Wuhan 430080, Hubei,
China)

Abstract: The law of element segregation of Ti, N, Mn and S, and the sequence of selective precipitation of TiN and MnS
inclusions during solidification of molten steel of SWRH82A are studied on the basis of thermodynamics. The origin of
large TiN inclusions which affect the titanium inclusions point penalty in SWRH82A wire rod is analyzed based on the
research on the distribution characteristics of MnS and large size of TiN inclusions observed on metallographic specimen
of SWRH82A steel wire rod. The solidification segregation ratio of Ti is far more than that of N, and the solidification
segregation ratio of S is far more than that of Mn. In the range of cooling rate of the continuous casting production,
the cooling rate of solidification has little effect on the segregation ratios of Ti , N, Mn and S. MnS inclusions will
precipitate earlier than TiN inclusions during solidification of the molten steel of SWRH82A. The large TiN inclusion
which is wrapped by MnS in the SWRH82A wire rod may be foreign inclusions and it is not precipitated product during
solidification in the molten steel of SWRH82A.
Key words: tire cord steel of SWRH82A; TiN inclusions; solidification segregation

SWRH82A is a kind of high strength steel
material used for making meridian wire of tyres for
passenger cars. The titanium inclusions in wire rod
heavily affect its drawing process property. In order
to control the precipitation of titanium inclusions in
wire rod, the strict steelmaking and refining process
measures are put into effect in steel plant to try to
remove impurity elements such as Ti and N from
molten steel to a limit content. However, during the
metallographic testing of SWRH82A steel wire rod
it can usually be found that the size of large TiN
inclusions can reach 6–8 μm[1, 2]. The conditions of the
precipitation of TiN inclusions during solidification
in tire cord steel are analyzed on the basis of
thermodynamics and kinetics from Ref. [3], but the
reason for the formation of large titanium inclusions in
wire rod lacks a full understanding so far. Combined
with actual case of SWRH82A rod coil, the origin
of large TiN inclusions in SWRH82A wire rod is
analyzed based on the thermodynamic prediction on
sequence of selective precipitation of TiN and MnS
inclusions during solidification of molten steel of
SWRH82A and the distribution characteristics of
MnS and large size of TiN inclusions observed on
metallographic specimen of SWRH82A steel wire rod.
1 Thermodynamics for Precipitation of TiN
and MnS inclusions
1.1 Solidification segregation of Ti, N, Mn and S in
SWRH82A
The chemical compositions of SWRH82A wire
rod are shown in Table 1.

Table 1 Chemical compositions of SWRH82A mass%

C Si Mn Ti P S N T.O
0.82 0.20 0.50 0.0006 0.010 0.0080 0.004 0.0022

The liquidus temperature (T 1 ) and solidus Ts=1811–(175w[C]+20w[Si]+30w[Mn]+280w[P]+

temperature (T s ) of SWRH82A are calculated 575w[S]+40w[Ti]+160w[O]) (2)
according to Eq. (1) and Eq. (2)[4]. The Tl and Ts of SWRH82A having a chemical
Tl=1811–(65w[C]+8w[Si]+5w[Mn]+30w[P]+25w[S]+ compositions as shown in Table 1 are 1752.5 K and
20w[Ti]+90w[N]+80w[O]) (1) 1639.6 K based on Eq. (1) and Eq. (2).

Biography: Yue-dong JIANG, Doctor, Senior Engineer; E-mail: jiang_yuedong@sina.com

Corresponding Author: Zheng-liang XUE, Doctor, Professor, E-mail: xuezhengliang@wust.edu.cn

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 Genetic Analysis for Large TiN Inclusions in Wire Rod for Tire Cord Steel of SWRH82A

During the solidification of SWRH82A the sol- solidification temperature are shown in Table 2[7-9].
ubility of solute atoms dissolved in the phase of γ-Fe
sharply descends and continuously enriches between Table 2 Equilibrium partition coefficients and the
dendritic crystals to form a great segregation ratio on diffusion coefficients in the solid phase
the front of solidification. The segregation ratio w[j]· Elements k D/(cm2·s–1)
w[j0]–1 of element j can be calculated according to the Mn 0.78 0.055exp(–59600/RT)
Ohnaka formula[5]: S 0.035 2.4exp(–53400/RT)
w[ j ] βk Ti 0.30 0.15exp(–250000/RT)
= [1 − (1 − ) g ]( k +1) /(1− β k /(1+ β )) (3)
w[ j0 ] 1+ β N 0.48 0.91exp(–168600/RT)

4Dτ
β=
L2
In Eq. (3) and Eq. (4), w[j] is the mass percent
concentration (%) of solute element j in solidifying
front, w[j0] is the mass percent concentration (%) of
solute element j before the solidification of molten
steel; k is the equilibrium distribution coefficient of
solute element j between molten steel and solid phase;
g is solidification ratio or solid fraction; D is the
diffusion coefficient (cm2·s–1) of solute element j in
solid phase; L is the second dendrite spacing (μm); τ is
the local solidification time (min).
The second dendrite spacing L is a function of
cooling rate Rc (K·min–1)[6]:
=L 688 × Rc −0.36 (5)
The local solidification time τ can be expressed as:
T −T
τ= l s (6)
Rc
In Eq. (6), Tl and Ts are the liquidus and solidus
temperature (K) of steel, respectively. By substitution
of Eq. (5) and Eq. (6) into Eq. (4) it can be obtained:
4 D(Tl − Ts )
β=
6882 × Rc0.28
For SWRH82A, the equilibrium partition coe-
fficients k of Mn, S, Ti and N between liquid steel and
γ-Fe and the diffusion coefficient D in solid phase at
(4) By substitution of the diffusion coefficient of
elements into Eq. (7), the value β of each element can
be calculated based on Eq. (7). According to Eq. (3),
it can be obtained that the relationships between the
solidification segregation ratio of Ti, Mn, N, S and
solidification ratio (g) at different cooling rates, as
shown in Fig. 1.
As shown in Fig. 1, with the increase of solidif-
ication ratio, the segregation of elements becomes
more and more serious. If the solidification ratio is
more than 0.97, Ti and S show a strong segregation
tendency. In contrast, the segregation of Mn and N
is relatively small. Therefore, although the average
content of Ti, N and S in molten steel is very low, it
may be still possible for TiN and MnS inclusions to
precipitate at solidification end due to the effect of
segregation. Furthermore, when the solidification
cooling rate increases from 60 to 1200 K·min–1, it has
little effect on solidification segregation ratio of Ti,
Mn, N and S.
1.2 Thermodynamic conditions of precipitating TiN
(7)
and MnS inclusions in the front of solidification of
SWRH82A
Due to the solidification segregation of the solute
elements during solidification, Ti, N, Mn and S are

800
-1
120 Ti: 60 K·min S: 60 K·min
-1

Ti: 1200 K·min

-1 700 S: 1200 K·min
-1

-1 -1
100 Mn: 60 K·min N: 60 K·min
-1 600
-1
Mn: 1200 K·min N: 1200 K·min
w（ j ）/ w（ j 0 ）
w（ j ）/ w（ j 0 ）

80 500

400
60

300
40
200

20 100

0 0
0.5 0.6 0.7 0.8 0.9 1.0 0.5 0.6 0.7 0.8 0.9 1.0

Solidification ratio（g） Solidification ratio（g）

Fig. 1 Relationship between segregation ratio of Ti, Mn, N, S and solidification ratio

92
 Genetic Analysis for Large TiN Inclusions in Wire Rod for Tire Cord Steel of SWRH82A

continuously enriched in the solidifying front, when QTiN=fTi·fN·w(Ti)·w(N) (11)

the activity products of Ti-N and Mn-S are greater QMnS=fMn·fS·w(Mn)·w(S) (12)
than the balanced activity products of TiN and MnS In Eq. (11) and Eq. (12), f Ti, f N, f Mn and f S are
precipitation, TiN and MnS inclusions will precipitate the activity coefficients of Ti, N, Mn and S at the
according to the following formula[10]: temperature of solidifying front, which can be
[Ti]+[N]=TiN(s) lgKTiN=4.01–13850/T (8) calculated by Eqs. (13) to (16)[11,12]:
[Mn]+[S]=MnS(s) lgKMnS=5.02–11625/T (9) lgfTi=(2557/Ts-l–0.365)lgfTi(1873) (13)
In Eq. (8) and Eq. (9), K TiN and K MnS are the lgfN=(3280/Ts-l–0.75)lgfN(1873) (14)
equilibrium constant of TiN and MnS precipitation, lgfMn=(2538/Ts-l–0.355)lgfMn(1873) (15)
which are only related with the temperature T s-l of lgfS=(2538/Ts-l–0.355)lgfS(1873) (16)
solidifying front. The temperature Ts-l of solidifying In Eq. (13) to Eq. (16), f Ti(1873), f N(1873), f Mn(1873)
front is calculated as follows[5]: and fS(1873) are the activity coefficients of elements Ti,
T0 − Tl N, Mn and S at 1873 K, respectively, which can be
Ts −=l T0 −
T −T (10) calculated according to the molten steel composition
1− g l s
T0 − Ts and the interaction coefficients of elements at 1873 K.
In Eq. (10), T0 is the melting point (1811 K) of lg fi (1873) = ∑ eij w( j ) (17)
pure iron. The actual activity products of Ti-N and The interaction coefficients of elements at 1873 K
Mn-S on the front of solidification are: are shown in Table 3[11, 12].
j
Table 3 Interaction coefficients of elements ei at 1873 K
Elements C Mn N O P S Si Ti
N 0.13 –0.02 0 0.05 0.045 0.007 0.047 –
Ti –0.19 –0.43 –2.03 –1.8 – –0.11 2.1 0.013
Mn –0.07 – –0.091 –0.083 –0.0035 –0.048 – –
S 0.11 -0.026 0.01 –0.27 0.029 –0.028 0.063 –0.072

By the chemical composition of SWRH82A and
the relationship between solute element segregation
ratio and solidification ratio, the actual content of
every solute element on the front of solidification,
and actual liquidus and solidus temperature in this
content of every solute elements can be obtained
when the solidification ratio of molten steel is g.
Through substituting the actual content of every solute
element into Eq. (17), the actual activity coefficients
of Ti, N, Mn and S can be calculated at the different
solidification ratios of SWRH82A at 1873 K. Then
the actual activity coefficients fTi(Ts-l), fN(Ts-l), fMn(Ts-l) and
solidification ratios and different temperatures of
solidifying front can be calculated.
Arranging the calculatd results, the thermodynamic
conditions of TiN and MnS precipitation on the front of
solidification can be obtained as shown in Fig. 2.
As shown in Fig. 2, because of solidification seg-
regation of solute elements, and the liquidus tempe-
rature and solidus temperature decrease originated from
this solidification segregation of solute elements, TiN
8
1 lgQTiN
6 2 lgKTiN
lgKTiN, lgKMnS lgQTiN, lgQMnS

3 lgKMnS
f S(Ts-l) at different solidification ratios and different 4 4 lgQMnS
temperatures of solidifying front can be calculated by
2
Eqs. (13) to (16). According to Eq. (3), the equation of
actual contents of Ti, N, Mn, and S of molten steel on 0
4

the front of solidification can be expressed as: -2

3
βk
) g ]( k +1) /(1− β k /(1+ β )) (18)
2
w[=j ] w[ j0 ] ⋅ [1 − (1 − -4
1+ β 1
By substituting the actual content of each -6
0.5 0.6 0.7 0.8 0.9 1.0

elements, and f Ti(Ts-l) , f N(Ts-l) , f Mn(Ts-l) and f S(Ts-l) into Solidification ratio（g）
Eqs. (11) and (12), the actual activity products of Fig. 2 Thermodynamics to precipitate TiN and MnS
Ti and N (QTiN), and of Mn and S (QMnS) at different during solidification of steel SWRH82A

93
 Genetic Analysis for Large TiN Inclusions in Wire Rod for Tire Cord Steel of SWRH82A
and MnS inclusions precipitated gradually during the
solidification. When the solidification ratio reached 0.6,
MnS inclusions first precipitated from the dendrites,
but the TiN inclusions would not precipitate until the
solidification ratio reached 0.90. In other words, MnS
inclusion will precipitate earlier than TiN inclusion
during the solidification of SWRH82A on the basis of
thermodynamics.
2 Genetic Analysis on Large TiN Inclusions
The SWRH82A wire rod (φ5.5 m) with the
composition shown in Table 1 is cut along the
S Ka1
Ti Ka1
Fig. 3 TiN covered by MnS inclusion detected from SWRH82A wire rod
of TiN inclusions. But in Fig. 3 the core of the
complex phase is TiN, and MnS inclusions precipitated
on the outside of the core. That is to say, TiN inclusion
exists first, then the MnS inclusion precipitates. From
the size of TiN inclusion, the large particles of TiN
inclusion in SWRH82A is likely a foreign inclusion,
instead of precipitates in the solidification process.
3 Conclusions
(1) Thermodynamic calculations showed that MnS
inclusions already precipitate before the precipitation
of TiN inclusions in the solidification process of
SWRH82A. MnS inclusions first precipitate from the
dendrites while the solidification ratio reaches 0.6,
but the TiN inclusions will not precipitate until the
solidification ratio reaches 0.90.
(2) The large particles of TiN inclusions which
are wrapped by MnS in wire rod of SWRH82A may
be a foreign inclusion but not the precipitated products
during solidification in molten steel.
The financial support from the Science Research
Plan (201210321098) of Wuhan Science and
94
longitudinal direction, then grinded and polished into
metallographic samples. The complex phase inclusions
that are observed and analyzed by SEM and EDS are
shown in Fig. 3. It is found that the light gray inclusion
in center is TiN with the size of 8 μm×4.5 μm, MnS
inclusion is wrapped on the outside from the surface
scanning analysis of the complex phase inclusions.
From above thermodynamic calculation, it can
be seen that for the molten steel with the composition
as shown in Table 1 TiN inclusions cannot precipitate
until the end of solidification process, and MnS
inclusion already precipitated before the precipitation
Mn Ka1
N Ka1_2
Technology Bureau, China is gratefully acknowledged.
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