Results in Physics 16 (2020) 102929

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Results in Physics
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Study of precipitation and growth processes of Ti-bearing inclusions in tire T

cord steel
⁎ ⁎
Ning Lia, Lu Wanga,b, , Zheng-Liang Xuea,b, , Cheng-Zhi Lib, Ao Huanga, Fang-Fang Wangc
a
The State Key Laboratory of Refractories and Metallurgy, Wuhan University of Science and Technology, Wuhan 430081, Hubei, China
b
Key Laboratory for Ferrous Metallurgy and Resources Utilization of Ministry of Education, Wuhan University of Science and Technology, Wuhan 430081, Hubei, China
c
School of Materials Science and Engineering, Beihang University, Beijing 100191, China

A R T I C LE I N FO A B S T R A C T

Keywords: Precipitation behavior and growth kinetics of Ti-bearing inclusions in SWRH 92A tire cord steel were analyzed in
Thermodynamics the present work. The calculated results showed that higher cooling rate would lead to a higher precipitation
Kinetics ratio of solution elements and make the precipitation time of inclusions earlier. However, both TiCyN1−y (a
Tire cord steel continuous solid solution between TiC and TiN, y denotes the molar ratio of TiC in TiCyN1−y) and TiN could only
Ti-bearing inclusions
precipitate in the two-phase region at the very late stage during the solidification processes, with the solid
fraction exceeds 0.99. The precipitation time of TiCyN1−y was a little earlier than that of TiN as well as the value
of y in the range of 0.1577–0.1617 (cooling rate: 0.5–2 K/s) was also obtained. Particle size of Ti-bearing
inclusions decreased with the increasing cooling rate and were within the range of 1.5–6.5 μm under the cal-
culated conditions, which accorded well with the size observed by the FE-SEM (field emission scanning elec-
tronic microscope). Increasing the contents of both N and Ti could lead to an earlier precipitation time of Ti-
bearing inclusions and make the particle size bigger, while the effect of N is much larger than that of Ti. The
results obtained by the adopted model were in well consistent with those of the statistical analysis. This work
may give an important guidance on the understanding of the precipitation and growth processes of Ti-bearing
inclusions in tire cord steel.

Introduction have been proposed by the internationally recognized companies (BE-

Tire cord steel possesses high toughness and strength and thus is one
of the most important framework materials of automobile tires [1].
Considering lightweight and security, the compositions of tire cord steel
have improved from previously used hypo-eutectoid types (SWRH 62A
and 67A; about 1750 MPa) to current hyper-eutectoid types (SWRH
72A and 82A; about 1870 MPa) [2]. Nowadays, studies on ultra-high
strength level of tire cord steel (SWRH 92A and 95A) have drawn more
and more attentions.
Ti-bearing inclusions, such as titanium nitride (TiN) and titanium
carbonitride (TiCyN1−y), that exist in tire cord steel have seriously
detrimental effects on the drawing and fatigue performances [3]. Ti-
bearing inclusions have a regular cubic-shaped morphology with a size
of 1.5–4 μm, as shown in Fig. 1, and its color generally changes from
golden-yellow to brick-red along with varying carbon content [4]. The
larger the Ti-bearing inclusion is, the more serious deterioration of the
tire cord steel would occur during the drawing and rope stranding
processes. Therefore, the testing and penalty point evaluation system
KAERT) in order to judge the tire cord steel rods, as shown in Eq. (1) [5]
. For example, if the total penalty points of tire cord steel rods exceeds
the threshold value (about 23), the material products will be rejected or
downgraded [6].
Q = 8N1 − 4μ + 19N4 − 9μ + 47N > 9μ + a (1)
where N1−4μ, N4−9μ, and N > 9μ are the amounts of Ti-bearing inclu-
sions that particles size are in the range of 1–4 μm, 4–9 μm, and bigger
than 9 μm, respectively; a is the constant that depends on steel types.
To reduce or avoid the formation of Ti-bearing inclusions in molten
steel, it is necessary to understand their precipitation behavior and
growth process first during the solidification process. At present, many
models have been proposed to analyze these issues, such as coupled
models [7–9] or traditional classical models [10–12]. As for the latter
(which were the focuses of this paper and will be described detailedly in
the following section), although numbers of relevant researches have
been reported in recent decades, the results of the precipitation beha-
vior and growth process for Ti-bearing inclusions were still debated or

⁎
Corresponding authors at: The State Key Laboratory of Refractories and Metallurgy, Wuhan University of Science and Technology, Wuhan 430081, Hubei, China.
E-mail addresses: wanglu@wust.edu.cn (L. Wang), xuezhengliang@wust.edu.cn (Z.-L. Xue).

https://doi.org/10.1016/j.rinp.2020.102929
Received 12 November 2019; Received in revised form 5 January 2020; Accepted 5 January 2020
Available online 13 January 2020
2211-3797/ © 2020 The Authors. Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND license
(http://creativecommons.org/licenses/BY-NC-ND/4.0/).
N. Li, et al. Results in Physics 16 (2020) 102929

Fig. 1. Images of Ti-bearing inclusions in SWRH 82A tire cord steel obtained by: (a) polishing treatment; (b) non-solution electrolytic [4].

even contradictory. For example, some references concluded that TiN w[i]/ w[0i] = [1 − (1 − ki ) g ]−1 (2)
was precipitated in the two-phase zone at the late stage during the
solidification process [13,14], while others reported that in the solid wherew[i]andw[0i] arethe instantaneous and initial concentrations of so-
phase zone [15]. Influences of solute elements on the particle size of lute element i, respectively; ki is the equilibrium distribution coefficient
TiN inclusion, sometimes, were also different. Some papers [3,16] of solute element between liquid and solid phases; herein, kC = 0.34,
thought that increasing the content of element Ti will lead to a bigger kN = 0.48, kTi = 0.3; g is the solid fraction, which is a function of the
particle size of final TiN inclusion; while Lei et al. [17] concluded that interfacial temperature T, as shown in Eq. (3) [19].
content of element Ti had litter impact on it. Lei et al. [17] also reported 1811 − TL
that cooling rate had no obvious effect on the segregation ratios of both T = 1811 − TL − TS
1− ·g (3)
N and Ti, and related researches on the precipitation behavior of Ti- 1811 − TS

CyN1−y inclusion were lacking in his work. Therefore, more detailed

where TL and TS are the liquidus and solidus temperatures of the stu-
researches should be done to further solve these problems with the
died steel, respectively; 1811 is the melting point of pure Fe (K).
consideration of traditional classical models.
Usually, Eq. (2) is not accurate during the solidification process, espe-
In this work, the thermodynamic of precipitation behavior and
cially for these elements with larger atomic mass, such as Ti, due to the
growth processes of Ti-bearing inclusions (TiN and TiCyN1−y) were
low diffusion velocity. On the contrary, Scheil model [11] is a non-
analyzed according to the model calculation. Industrial manufacture of
equilibrium solidification model which assumes that solute element is
SWRH 92A tire cord steel was used as the analyzed material, the cor-
completely diffused in liquid phase but has no diffusion in solid phase,
responding chemical composition is shown in Table 1. Effects of dif-
as expressed by Eq. (4). However, Eq. (4) could not adequately estimate
ferent parameters, such as secondary dendrite arm spacing, cooling
the final element concentration, especially at the late stage. For ex-
rate, and element concentration on the precipitation mechanism and
ample, when the solid fraction near to 1, the value of segregation ratio
growth kinetics of Ti-bearing inclusions were illustrated. Corresponding
of solute element will be infinite, which is obviously not consistent with
experimental data were also obtained in order to verify the calculated
the common sense.
results.
w[i]/ w[0i] = (1 − g )ki− 1 (4)
Micro-segregation models
Due to the fact that the inverse diffusion of solute elements have an
significant influence on the segregation of solute elements, and thus
Previous work
affecting the precipitation behavior of Ti-bearing inclusions [20,21].
So, in order to achieve a more realistic representation, Brody and
Due to the decrease in the solubility of solute elements from liquid
Flemings [12] proposed a general form, in which finite inverse diffu-
to solid phases during the solidification process, solute redistribution
sion, at least in the solid phase, was considered, as shown by Eq. (5),
and micro-segregation would occur inevitability, which would further
where ϕ is the inverse diffusion coefficient and in the range of 0–1.
lead to the macro-segregation in the billet depending on the casting
conditions [16,18]. Up to date, many micro-segregation models w[i]/ w[0i] = [1 − (1 − ϕki ) g ](ki− 1)/(1 − ϕki) (5)
[10–12] have been developed to predict the concentration change of
solute element In Eq. (5), ϕ may have different expressions, such as Eqs. (6) [10]
Lever-rule model [10] is an equilibrium solidification model which and (7) [12]. However, model with Eq. (6) lacks of actual physical basis
assumes that solute elements are completely diffused in both liquid and for intermediate value of ϕ; Eq. (7) is also not physically reasonable
solid phases, as expressed by Eq. (2). when α bigger than 0.5 and ϕ exceeds 1.

Table 1
Chemical composition of analyzed SWRH 92A tire cord steel (mass%).
Solute elements C Si P S O Mn N Ti

Content/(mass%) 0.9203 0.1812 0.0179 0.0064 0.0018 0.5104 0.0043 0.0005

2
N. Li, et al. Results in Physics 16 (2020) 102929

1 1
ϕ = 2α ⎡1 − exp ⎛ - ⎞ ⎤ − exp ⎛ - ⎞
⎣ ⎝ α ⎠⎦ ⎝ 2α ⎠ (6)

ϕ = 2α (7)

To solve the above problems, modified Ohnaka model [22] is

adopted in this work, as seen in Eq. (8), which not only satisfied the
scale of ϕ in the range of 0–1, but also possessed actual physical basis.
α
ϕ=
1+α (8)

In all of the models mentioned above, α is the Fourier parameter,

which involves the diffusion coefficient Di (cm2/s), secondary dendrite
arm spacing L (μm), and the local solidification time τ (s), as seen in Eq.
(9).
4Di τ
α =
L2 (9)

Values of Di for C, N, and Ti can be calculated by Eqs. (10)–(12),

respectively [23–26]; local solidification time τ is calculated by Eq.
(13); Rc is the cooling rate (K/s). However, as to L, it has different
algebraic expressions, which are analyzed separately in the subsequent
part.
143511
DC = 0.0761 exp ⎛− ⎞
⎝ RT ⎠ (10)

168600
D N = 0.91 exp ⎛− ⎞
⎝ RT ⎠ (11)

250000
D Ti = 0.15 exp ⎛− ⎞
⎝ RT ⎠ (12)

TL − TS
τ =
Rc (13)

Secondary dendrite arm spacing

Fig. 2. Comparison of various equations for the secondary dendrite arm spa-
By summarizing various experimental data, four kinds of expres- cing.
sions for L have been proposed by metallurgists, as listed in Eqs. (14)
[27], (15) [28], (16) [29], and (17) [30], which are defined as L1, L2, Thermodynamic and kinetics analysis
L3, and L4, respectively, in this paper.
Segregation ratio of solute elements
⎧ 148Rc −0.38 0 ⩽ w[0C ] < 0.53
L1 = 0
⎨[21.53 − 9.4·w[0C ] ·τ 0.4 + 0.08·w[C] ] 0.53 ⩽ w[0C ] < 1.5 To calculate the segregation ratios of solute elements, TL and TS are
⎩ (14)
needed first. For this purpose, Eq. (18) [31] was employed in this paper.
0 −0.49350 ⩽ w 0 < 0.15 After the calculation, TL = 1748 K and TS = 1636 K are obtained.
⎧ [169.1 − 720.9·w[C ] ]·Rc [C ]
L2 = − 1.996·w[0C ] 0
⎨143.9·Rc −0.3616 0
·w[C ] 0.5501
w[C ] ⩾ 0.15 ⎧ TL=1811 − 65w[C] − 8w[Si] − 30w[P] − 25w[S] − 80w[O] − 5w[Mn] − 90w[N]
⎩ (15)
⎪
⎪ − 20w[Ti]
L3 = [23.7 − 13.1·w[01/3 1/3 0.09 < w 0 < 0.7
C ] ]· τ [C ] (16) ⎨ TS=1811 − 175w[C] − 20w[Si] − 280w[P] − 575w[S] − 160w[O] − 30w[Mn]
⎪
L4 = 688·Rc −0.36 (17) ⎪ − 40w[Ti]
⎩
To achieve a more intuitive effect, Eqs. (14) to (17) are plotted as (18)
diagrammatic forms at the cooling rates of 0.5 K/s and 1 K/s, as de- Content of carbon in SWRH 92A tire cord steel is about 0.9203 mass
picted in Fig. 2. As for Eq. (14), the value of L1 kept constant when the %, so L3 is not applied for the calculation of L in this paper. Therefore,
carbon content was below 0.53 at a fixed cooling rate, while when the L1, L2, and L4 are used for the analysis of the segregation ratios of solute
carbon content was above 0.53, the value decreased gradually. As for elements. The results of segregation ratios of C, N, and Ti obtained by
Eq. (15), the value of L2 decreased steeply with the increasing carbon using various equations [corresponding to L1, L2, and L4] are shown in
content from zero to 0.15; and then increased with increasing carbon Fig. 3. The calculated results showed that segregation ratios of different
content until 0.59; while from 0.59 to 1.5, L2 reduced again with in- solute elements all increased with the increasing solid fraction, and the
creasing carbon content, as seen in Fig. 2(a). As for Eq. (16), the value segregation ratio obtained using L4 was still much larger than those
of L3 continually decreased in the application scope of 0.09 to 0.7. As using L2 and L1, the segregation ratios of C and N are relatively small.
for Eq. (17), however, the value of L4 was considered as constant at a For example, segregation ratio of C is always below 3.4 (seen Fig. 3a)
fixed cooling rate. Furthermore, the values of L for L1, L2, L3, and L4 are and that of N below 2.2 (seen Fig. 3b). As for Ti, the segregation ratio is
all decreased with the increasing cooling rates. quite high, especially at the late period where the solid fraction near to

3
N. Li, et al. Results in Physics 16 (2020) 102929

(a) 3.4 calculated results are in well agreement with other papers [5,32]; in
L1 -1 K/s addition, it was also experimentally verified by Fu et al. [33], who
3.2 L2 -1 K/s concluded that higher cooling rate was beneficial for the precipitation
3.0 L4 -1 K/s of TiN inclusion and that the formed particle could precipitate from
melt earlier if the cooling rate was sufficient (in this case, the size of
2.8
inclusions will be very small and even cannot be detected) [33].
w[C]/w[C]
0

2.6
Precipitation condition of Ti-bearing inclusions
2.4

2.2 As is known to all, if the actual solubility product (defined as

lgKij = lgw[i]⋅w[j]) of Ti-bearing inclusions larger than that of the
2.0
equilibrium value (defined as lg K ijθ = lg w[θi] ·w[θj] ), Ti-bearing inclusions
1.8 will precipitate. The actual values can be calculated by the adopted
Ohnaka model [22] with the application of L4 and L2; the equilibrium
1.6 values can be obtained based on the chemical reactions for the for-
0.50 0.55 0.60 0.65 0.70 0.75 0.80 0.85 0.90 0.95 1.00 mation of TiN and TiC [see Eqs. (19) and (20), respectively] in molten
Solid Fraction, g steel, which could be further transformed into equations (21) and (22),
respectively [32,34]. The compared results of equilibrium solubility
(b) 2.2
L1 -1 K/s product with the actual values of TiN and TiC are shown in Fig. 5. It can
L2 -1 K/s be found that TiN will precipitate at the very late stage during the so-
L4 -1 K/s lidification process, for a solid fraction of 0.9974, 0.9972, and 0.9969 at
2.0
the cooling rates of 0.5, 1, and 2 K/s, respectively. The larger the
cooling rate is, the earlier the precipitation time will be, as observed in
the inset of Fig. 5(a). However, as for TiC, the values of lgKTiC (for all
w[N]/w[N]
0

1.8 the three cooling rates) are always smaller than that of
θ
lg KTiC throughout the solidification process, as shown in Fig. 5(b),
which indicates that TiC will not precipitate in the two-phase region.
1.6 θ
[Ti] + [N ] = (TiN )inclusion ΔG19 = −291000 + 107.91T (19)
θ
[Ti] + [C] = (TiC )inclusion ΔG20 = −157524 + 88.362T (20)
1.4
θ 15229
lg KTiN = 5.6778 −
T (21)
0.50 0.55 0.60 0.65 0.70 0.75 0.80 0.85 0.90 0.95 1.00
Solid Fraction, g θ 8200
lg KTiC = 4.6147 −
T (22)
(c) L1 -1 K/s
140 On the other hand, TiN and TiC have the same NaCl face-cubic
L2 -1 K/s structure and similar lattice constants (0.4241 nm vs. 0.4327 nm for
120 L4 -1 K/s TiN and TiC, respectively), they also show the property of infinite
mutual solubility with each other, so it is possible for them to form the
100 complex carbonitride [32,35–37]. Herein, we denote it as TiCyN1−y, a
continuous solid solution formed by replacing parts of N in TiN crystal
w[Ti]/w[Ti]
0

80 with C atoms, where y means the molar ratio of TiC in TiCyN1−y. The
reaction for the formation of TiCyN1−y can be written as Eq. (23). For
60 simplicity, Eqs. (24) and (25) were used for the thermodynamic cal-
culation, which have been widely used in other references [6,32,38,39].
40 Combing Eqs. (24) and (25) as well as the above results, it is concluded
that TiCyN1−y could also precipitate at the very late stage during the
20 solidification process, with the solid fractions of 0.9964, 0.9961, and
0.9959 at the cooling rates of 0.5, 1, and 2 K/s, respectively, as shown
0 in Fig. 6. Furthermore, the molar ratio of TiC in TiCyN1−y could also be
0.50 0.55 0.60 0.65 0.70 0.75 0.80 0.85 0.90 0.95 1.00
deduced, at the corresponding values of 0.1577, 0.1598, and 0.1617,
Solid Fraction, g
respectively. By comparing the values of solid fraction for the pre-
Fig. 3. Comparisons of segregation ratios of solute elements C, N, and Ti ob- cipitation of TiCyN1−y with those of TiN, it could found that TiCyN1−y
tained by using L1, L2, and L4: (a) C; (b) N; (c) Ti. precipitate a little earlier than that of TiN, the corresponding results are
listed in Table 2.

1 (about 140 when L4 was used, as seen in Fig. 3c). [Ti] + y [C ] + (1 − y )[N ] = (TiCy N1 − y )inclusion (23)
Effects of cooling rates (0.5, 1, and 2 K/s) on the segregation ratios
θ
of solute elements C, N, and Ti are also analyzed, as displayed in Fig. 4. w[Ti]·w[N ] = KTiN = (1 − y ) KTiN (24)
Segregation ratios of C and N are both increased with the increasing
θ
cooling rate when L4 was used; as for Ti, however, the change was w[Ti]·w[C ] = KTiC = yKTiC (25)
unobvious, as observed in Fig. 4(a), (b), and (c). When L2 was used, the However, when L2 was used for the calculation, it was found that
results were opposite, changes of segregation ratios of solute elements C actual solubility products of both TiN and TiC were always smaller than
and N were unobvious with the increasing cooling rate, while Ti ob- that of equilibrium values throughout the solid-liquid two-phase zone
viously increased, as observed in Fig. 4(A), (B), and (C). The current at various cooling rates, as shown in Fig. 7, which indicated that the

4
N. Li, et al.
Fig. 4. Effect of cooling rates on the segregation ratios of solute elements C, N, and Ti obtained by using: (a), (b), and (c) L4; (A), (B), and (C) L2.
thermodynamic conditions for the precipitation of both TiN and TiC
were not satisfied, and so TiN and TiC inclusions would not precipitate
in this case. The thermodynamic condition for the precipitation of Ti-
CyN1−y inclusions is also not satisfied (the calculated results are not
given). Since the segregation ratios of C, N, and Ti were the lowest
when L1 was used for the calculation among these three cases, as ob-
served in Fig. 3, it can be reasonably inferred that TiC, TiN, and Ti-
CyN1−y will not precipitate when L1 was used. Generally, the growth
kinetics conditions in solid-liquid two-phase zone are prior to those in
the solid phase, so it can be deduced that L4 can best explain the for-
mation of larger Ti-bearing inclusions detected in the tire cord steel
5
Results in Physics 16 (2020) 102929
rods (see Fig. 1), which would be further verified by the following ki-
netics calculation and experimental data.
Growth kinetic of Ti-bearing inclusions
As mentioned above, both TiCyN1−y and TiN inclusions would
precipitate at the very late stage (for a solid fraction bigger than 0.99
when L4 was used) during the solidification process. Since the value of y
in TiCyN1−y is small (in the range of 0.1577 to 0.1677), and so
TiCyN1−y could be considered as a high N compound. That is to say, the
main inclusion precipitated in tire cord steel is still TiN. Therefore, the
N. Li, et al. Results in Physics 16 (2020) 102929

Table 2
Precipitation conditions of Ti-bearing inclusions in molten steel.
Ti-bearing Rc (K/s) Secondary dendrite arm Solid Value of y
inclusions spacing/(μm) fraction

L4 L2 L1

TiN 0.5 ✓ × × 0.9974 –

1 ✓ × × 0.9972 –
2 ✓ × × 0.9969 –
TiC 0.5 × × × – –
1 × × × – –
2 × × × – –
TiCyN1−y 0.5 ✓ × × 0.9964 0.1577
1 ✓ × × 0.9961 0.1598
2 ✓ × × 0.9959 0.1617

Fig. 7. Comparison of equilibrium solubility products with the actual calcu-

lated values of TiC and TiN in the two-phase zone when L2 was used at different
Fig. 5. Comparisons of equilibrium solubility product with the actual values of cooling rates (0.5, 1, and 2 K/s).
TiC and TiN in two-phase zone when L4 was used at different cooling rates (0.5,
1, and 2 K/s). cooling rate Rc, as described by Eq. (27) [40,41]. Therefore, it is ne-
cessary to analyze the effect of Rc on the particle size of TiN inclusion.
16π σ 3Tl
ΔG o = · ·f (θ)
3 Hm2 ΔT 2 (26)

d ΔT ΔT 1
= ·
dR c Rc 1 + 2Tl − 3ΔT Af (θ) σ 3Tl
·
ΔT 2·(Tl − ΔT ) ΔHv2 κ (27)

In Eq. (26), ΔG o is the critical nucleate work (J); ΔT is the super-

Fig. 6. Thermodynamic condition for the precipitation of TiCyN1−y inclusion.
growth kinetics of Ti-bearing inclusions could be analyzed and focused
on TiN.
Critical nucleation work of TiN could be calculated by Eq. (26),
from which it can be known that the main factor affecting the nuclea-
tion of particle is the super-cooling degree, which depends on the local
cooling degree (K); σ is the interfacial free energy (J); Tl is the tem-
perature (K); f(θ) is the catalytic factor of the contact angle of the cri-
tical crystal nuclei with the undercooled melt; θ is the critical contact
angle (degree); and Hm is the solidification latent heat (J). In Eq. (27),
ΔHv is the fusion heat (J); κ is the Boltzmann’s constant (1.38 × 10−23
J/K); and A is the shape factor (3/16π for a spherical nucleus).
As mentioned above, segregation of solute elements N and Ti will be
occurred in the liquid phase zone between the secondary dendrite arm
spacing during the solidification process, and then the concentrations of
both N and Ti will be enriched. Once the actual solubility product of N
and Ti (lg KTiN = lg w[Ti]·w[N ]) bigger than the equilibrium value
θ
(lg KTiN = lg w[θTi] ·w[θN ] ), TiN inclusion will be precipitated and growth
gradually. Thus, it can be inferred that the values of (w[i] − w[θi] ) was the
driving force for the growth of TiN particle, where i represented the
solute element N or Ti. However, solute elements N and Ti will also
diffuse back from the secondary dendrite arm spacing to the molten
steel, which will make the value of (w[i] − w[θi] ) decreased, and so the
driving force for the growth will be reduced. Therefore, the larger the

6
N. Li, et al. Results in Physics 16 (2020) 102929

diffusion coefficient is, the lower the value of (w[i] − w[θi] ) will be. Due to
the fact that the diffusion ability of N is much bigger than that of Ti in
molten steel [seen Eqs. (11) and (12)] and the segregation of Ti is much
larger (as seen in Figs. 3 and 4), and so the enrichment of Ti is easier in
the solidifying front. In other words, concentration of Ti is high enough
in the solid–liquid interface and then the diffusion of solution element
N will be the rate-controlling step for the growth of TiN particle, as
shown in Eq. (28) [13], which was also adopted for the calculation of
TiN particle size in other references [14,16,41].
dr Ms ρ
r = · m ·D N (w[N ] − w[N]
θ
)
dt 100Mm ρs (28)

Integrating Eq. (28), one can obtain,

1/2
Ms ρm
r=⎡ · ·D N ·(w[N ] − w[θN ] )·τ⎤
⎢ 50Mm ρ ⎥ (29)
⎣ s ⎦
where r (cm) is the radius of TiN particle; Ms (g/mol) and Mm (g/mol)
are the molar mass of TiN and molten steel, respectively; ρs (g/cm3) and
ρm (g/cm3) are the density of TiN and molten steel, respectively; w[N]
andw[θN ] are the mass fraction of element N in the solid-liquid interface
and in equilibrium with TiN, respectively, which can be calculated
based on equations (5) and (21), respectively; DN (cm2/s) and τ (s) are
the diffusion coefficient of element N and local solidification time, as
shown in equations (11) and (13), respectively.
According to Eq. (29), the relationship between particle size of TiN
and solid fraction at different cooling rates could be calculated (the unit
of r was converted from cm to μm for clarity), as shown in Fig. 8. From
Fig. 8 it can be seen that particle size of TiN inclusion increased gra-
dually as the solidification proceeds, and the growth rate of TiN at
lower cooling rate is larger than that at higher cooling rate. If con-
sidering radius r equals zero as the initial precipitation time, it can be
also found that higher cooling rate leads to an earlier precipitation
time, which is in well agreement with the above results (seen Fig. 5a).
Final particle size of TiN inclusion decreased with the increasing
cooling rate, which is consistent with the other references [18,42,43].
What is more, the final inclusion size are 3.63, 2.79, and 1.99 μm when Fig. 9. Effects of different initial concentrations of N and Ti on the particle size
the cooling rates are 0.5, 1, and 2 K/s, respectively, which are in well of TiN inclusion.
agreement with the results shown in Fig. 1 and the following experi-
mental sections.
molten steel can also contribute to an earlier precipitation time, as
In order to make a deeper understanding on the growth process of
shown in Fig. 9a. At a fixed initial Ti content (0.0005 mass%) and
TiN inclusion, effect of solute elements N and Ti on the particle size are
cooling rate (1 K/s), when the N contents were 0.00265, 0.0043,
also considered, and the calculated results are shown in Fig. 9. It can be
0.0086, and 0.0172 mass%, the solid fraction for TiN precipitate were
found that increasing the concentration of element N will lead to a
0.9989, 0.9972, 0.9914, and 0.9778, respectively. Effects of initial Ti
bigger particle size of TiN inclusion, and the increment of N content in
content on the particle size of TiN inclusion are similar to the case of N,
as shown in Fig. 9b. Whereas, effect of initial Ti content on the final
particle size of TiN inclusion is smaller than that of N, as can be ob-
served by comparing Fig. 9b with 9a; i.e., the final particle size of TiN
inclusion increased from 1.72 to 6.42 μm when N contents increased
from 0.00265 to 0.0172 mass% at the fixed Ti content (0.0005 mass%),
while the final particle size of TiN inclusion increased from 1.76 to
3.22 μm when Ti contents increased from 0.00025 to 0.002 mass% at
the fixed N content (0.0043 mass%), which could also demonstrate that
the diffusion of solute element N other than Ti was the rate-controlling
step for the growth of TiN inclusion. The current calculated results were
coincided with those reported by Cai et al.[3] and Ma et al.[16]; while
had a difference with that reported by Lei et al. [17], in which initial Ti
concentration had little effect on the final particle size of TiN inclusion
was concluded, the possible reasons may be due to different models or
different values of parameters, such as diffusion coefficient.

Experimental verification

Fig. 8. Relationship between particle size of TiN inclusion and solid fraction at To further verify the reasonability of the adopted Ohnaka model,
different cooling rates (0.5, 1, and 2 K/s). additional experiments were carried out in our group work [4]. Firstly,

7
N. Li, et al. Results in Physics 16 (2020) 102929

Fig. 10. Images of Ti-bearing inclusions obtained by the FE-SEM in the studied tire cord steel: (a) obtained by the polishing treatment; (b) obtained by the non-
solution electrolytic.

the SWRH 92A tire cord steel slabs were cut into an appropriate di-
mension size, about φ 5.5 mm × 10 mm; secondly, several rods were
ground by the abrasive paper (from 150 to 2000 meshes), and then
polished by the polishing machine; thirdly, other rods were electrolyzed
by the non-solution electrolytic method with a period of time (about
2 h), and then the anode slime were collected; finally, the samples
obtained by the above two routes (routes 2 and 3) were detected by the
field emission scanning electronic microscopy (FE-SEM; Nova 400 Na-
noSEM, FEI Corporation, American) and metallographic image analyzer
(KA-MIAS, Nanjing aokang analytical instrument Co., LTD, China).
Fig. 10 shows the images of Ti-bearing inclusions obtained by the
FE-SEM in the studied tire cord steel. As can be seen from Fig. 10a,
particle size of Ti-bearing inclusions are non-uniform, the larger is
about 4 μm and the smaller may be 2 μm; besides, the angular margin of
particles can be obviously seen, indicating that the formed Ti-bearing
inclusions were cubic structure, which can be further proved by
Fig. 10b (the Ti-bearing inclusion of Fig. 10b was obtained by the non-
solution electrolytic method).
Fig. 11 shows the typical images of existed Ti-bearing inclusions in
Fig. 12. Size distribution of Ti-bearing inclusions obtained by the optical mi-
the studied tire cord steel. From Fig. 11 it can be seen that the color of
croscopy in the studied tire cord steel [4].
precipitated Ti-bearing inclusions are golden-yellow or brick-red, which
suggest that the main components of inclusions are TiN and TiCyN1−y
[4]. To calculate the average size of Ti-bearing inclusions, 50 fields 4–5, and greater than 5 μm. The amounts of inclusions in the range of
including the inclusions are obtained and the analyzed results of size 2–3 μm occupied mostly, which accounts for about 34.5%. And the
distributions are showed in Fig. 12. The amounts of Ti-bearing inclu- average size of Ti-bearing inclusions was calculated to be about
sions in the range of below 1, 1–2, and 2–3 μm are gradually increased, 3.32 μm. The current experimental results (Figs. 10–12) are in well
and then gradually decreased for the particles size in the range of 3–4, agreement with those calculated by the Ohnaka model (equations (5)

Fig. 11. Images of Ti-bearing inclusions obtained by the optical microscopy in the studied tire cord steel.

8
N. Li, et al.
and (8)), as shown in Figs. 8 and 9, which indicated that adopted model
had some credibility and reasonable.
Conclusions
In this paper, the precipitation behavior and growth kinetics of Ti-
bearing inclusions in SWRH 92A tire cord steel were analyzed based on
the thermodynamic calculation, in which different parameters, such as
secondary dendrite arm spacing, cooling rate, and element concentra-
tion were discussed in detail. The following conclusions can be drawn.
(1) The influence sequences of secondary dendrite arm spacing on the
segregation ratio is: L4 > L2 > L1; segregation ratio of Ti is much
larger than that of C and N, which are all increased with the in-
creasing solid fraction, especially at the late stage during the soli-
dification process.
(2) Higher cooling rate could lead to a larger segregation ratio of solute
elements and make the precipitation time of Ti-bearing inclusions
earlier; while the particle size is decreased gradually as increasing
cooling rates.
(3) Precipitation time of TiCyN1−y is a little earlier than that of TiN,
which can act as a heterogeneous nucleation site for TiN. Molar
ratio of TiC in TiCyN1−y were in the range of 0.1577 to 0.1617 and
increased with the increasing cooling rates at the current condi-
tions.
(4) Increasing the initial concentrations of N and Ti would lead to an
earlier precipitation time and larger particle size of TiN inclusion;
however, the effect of N is much larger than that of Ti.
(5) The calculated particle size of Ti-bearing inclusions is in the range
of 1.5–6.5 μm, which is in well agreement with the size measured
by FE-SEM and metallographic image analyzer found in tire cord
steel samples.
CRediT authorship contribution statement
Ning Li: Conceptualization, Methodology. Lu Wang: Investigation,
Writing - review & editing. Zheng-Liang Xue: Supervision, Project
administration, Funding acquisition. Cheng-Zhi Li: Writing - review &
editing, Formal analysis. Ao Huang: Funding acquisition. Fang-Fang
Wang: Visualization, Funding acquisition.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influ-
ence the work reported in this paper.
Acknowledgment
The authors gratefully acknowledge the financial support for this
Results in Physics 16 (2020) 102929
work from the National Natural Science Foundation of China
(51874214), the Special Project of Central Government for Local
Science and Technology Development of Hubei Province
(2019ZYYD076), National Postdoctoral Program for Innovative Talents
funded project (BX20180023), and China Postdoctoral Science
Foundation Funded Project (2019M650424).
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