Process Metallurgy - Steelmaking

State of the Art in the Control of Inclusions in Tire Cord Steels - a Review
Lifeng Zhang

Department of Materials Science and Engineering, Norwegian University of Science and Technology, Trondheim, Norway

The control of inclusions in tire cord steels and techniques used in the production process are extensively reviewed. Inclusion and segre-
gation requirements for the tire cord steel are discussed. The deformability of an inclusion is significantly affected by its AI203 content. In-
clusions containing 20% AI20 3 has best deformability. The undeformable inclusions can be avoided by controlling the dissolved aluminum in
the steel. Low basicity slags favour the generation of deformable inclusions. When the basicity R (=CaO/Si0 2 ) = 0.8-1.5, the dissolved alu-
minum in the steel should be 1-5ppm to achieve 20% AI203 in inclusions. With R=1.0-1.4, in order to control [AI] in the range of 1-5ppm, the
slag should contain approximately 8% A1 203. The technologies to control inclusions in tire cord steels are reviewed including steel deoxidiz-
er choice, steel refining method, slag carry over from BOF to the ladle, ladle stirring practice, control of nitrogen pickup and caster curva-
ture. Control methods to decrease the central segregation in the tire cord steel are briefly reviewed, such as electromagnetic stirring during
continuous casting.

Keywords: Inclusions, Tire Cord Steel, Steel Refining, Tundish, Synthetic Slag Treatment

Inclusions and Clean Steel
Clean steel production is the key task of steelmakers. The
definition of "Clean Steel" depends on steel grades and
their end use, requiring some of the impurity elements, such
as oxygen, nitrogen, phosphorus, sulphur, hydrogen, and
sometimes even carbon, to some low levels and inclusions
small and few enough [1]. It is well known that the me-
chanical behaviour of steel is controlled to a large degree by
the volume fraction, size, distribution, composition and
morphology of inclusions and precipitates, which act as
stress raisers, and especially there should be no inclusions
in the casting above a critical size. Examples are shown in
Table 1 [2-7]. DI cans require [C] < 30 ppm, [N] < 30 ppm
and Total Oxygen (T.O.) < 20 ppm, and inclusions smaller
than 20!lm [3]. Bearing steels require T.O.<lOppm, and in-
clusions no larger than 15 urn [4,5,7]. Tire cord steel even
has stricter requirements due to its end use [5]. Non-metal-
lic inclusions in steel are termed as indigenous inclusions
and exogenous inclusions according to their sources. In-
digenous inclusions are deoxidation products, their compo-
sition mainly depending on the type of the deoxidizer, or
precipitated inclusions during cooling and solidification of
steel. Alumina and silica are the typical deoxidation inclu-
sions in the steel killed by Al and Si respectively. Alumina
inclusions are dendritic when formed in a high oxygen en-
vironment or clusters [8], and non-deformable during
rolling and later processing of the steel. Silicate inclusions,
generally spherical owing to being in a liquid or glassy state
in the molten steel, can also agglomerate into clusters [9],
and are normally deformable during steel rolling. Exoge-
nous inclusions arise primarily from the incidental chemical
(reoxidation) and mechanical interaction of liquid steel with
its surroundings (slag entrainment [10] and erosion of lin-
ing refractory), with the following common characteristics:
large size, compound composition! multiphase, small num-
ber and sporadic distribution in the steel. Exogenous inclu-
sions are always practice related and their size and chemi-
cal composition often lead to the identification of their
sources. Although the solidification morphology of inclu-
sions is important in steel castings, the morphology of in-
clusions in wrought products is largely controlled by their
mechanical behaviour during steel processing, i.e. whether
they are "hard" (non-deformable) or "soft" (deformable)
relative to the steel matrix [11]. Control of inclusion com-
position is also important due to the following reasons:
- Inclusions with special compositions may affect the con-
tinuous casting process, e.g. alumina inclusions induce
nozzle clogging;
- Inclusions with special compositions tend to be assimilat-
ed by the top slag;
- Inclusions with special compositions are non-deformable
during rolling and later processing of the steel thus in-
ducing serious problems, e.g. inclusions can induce

Table 1. Typical steel cleanliness requirements reported for various steel grades.

Steel product Maximum impurity fraction Maximum inclusion size

Automotive & deep-drawing sheet [C]s30ppm, [N]s30ppm [3] IOOllm [2, 3]
Drawn and ironed cans [C]s30ppm, [N]s30ppm, T.O.s20ppm [3] 20llm [3]

Line pipe [S]s30ppm [4], [N]s35ppm, T.O.s30ppm [5], [N]s50ppm [6] IOOllm [3]
Ball bearings T.O.slOppm [4, 7] I511m [5, 7]
Tire cord [H]s2ppm, [N]s4Oppm, T.O.sI5ppm [5] l Oum [5], 20llm [2]
Heavy plate steel [H]s2ppm, [N]30-40ppm, T.O.s20ppm [5] Single inclusion 13llm[3], Cluster IOOllm[3]
Wire [N]s6Oppm, T.O.s30ppm [5] 2Ollm[5]

158 steel research into 77 (2006) NO.3

 Process Metallurgy - Steelmaking

Table 2. Typical composition (wt.%) of the tire cord steel at Kobe steel [12, 13].

C Si Mn P S 0
Higher strength tire cord steel 0.80-0.85 0.15-0.30 0.40-0.60 0.020max 0.020max 0.0017
Conventional tire cord steel 0.70-0.75 0.15-0.30 0.40-0.60 0.020max 0.020max 0.0018

Figure 1. Typical inclusions (AI 13.40%, Si 44.24%, S 2.79%, K 11.28%, Ca 2.60%, Fe 25.70) observed on wire break [15].

breakage of wire steel (high carbon steel) during the 60

drawing process and cause crack formation in low carbon
sheet steels;
- Inclusions with special compositions may induce surface ~~o 0

flaw, fatigue failure, hydrogen induced cracking, and low

temperature embrittlement, etc. -....
'#.
50
~Dt r D
~~<>
~~
"
'o<>~l>1; 0
1t- r'''::---L--J
Q) 'b ooo.... <f>"........"" "
l> " "
.aIII
'~%~
40
Requirements of Inclusions in the Tire Cord
o°Cb ~
>
Steel III
Q)
"- <> "-
Steel tire cord has long been used as a reinforcement of
rubber products, because it can add excellent elasticity and
strength to the rubber, with typical compositions as shown
-III

0
c
30
Tensile strength
kgf/mm 2
00 0 1<>-----.
~
0
in Table 2 [12, 13]. There has been a great demand from tire :;: 0342 ~
u 20 I -
manufacturers to reduce tire weight by using less steel and ::::I
'a
o 335 ° 0

improve tire performance by using steel tire cords with Q) .6. 324
a:
higher breaking strength. The tensile strength of tire cord o 301
steel for automobile tire is required to be 3600 MPa, ideal- 10
ly even 5000MPa. The wire of the tire cord should be able
to be drawn from <I>5.5mm to <j>O.12-0.25mm. The breakage
of the tire cord wire during the drawing process is usually o
due to the presence of non-deformable inclusions with an o 5 10 15 20 25
incoherent boundary [12, 14], as shown in Figure 1 [15], or Undeformable inclusion size (pm)
the serious center segregation of some elements [16], or
Figure 2. Reduction of area values of weirs with different tensile
center porosity. "Non-deformable" is defined as that the ra- strength as function of the size of undeformable inclusions ap-
tio of length/width of an inclusion is smaller than 3 after hot peared on the tensile fracture interface [12].
rolling [17]. Larger non-deformable inclusions lower the
reduction of area values of wires, i.e. they entail more
breaks of the wire than small inclusions do, as shown in Steel size
Figure 2 [12]. Non-deformable inclusions are usually
spinels, calcium alurninates, and alumina. The non-de- Alumina

formable inclusion may induce the nucleation and growth

of voids, initiate ductile fracture during the manufacture of Silica
wire, and cause breakage of wire during final drawing. The
deformable inclusions are usually silicate or silico-alumi-
nates with size <4-5f.lm,depending on the detailed compo- .. 20!'JIl
Directionof rollingand drawing
sition of inclusions. Examples of inclusion deformation
during the drawing process of steel are shown in Figure 3 Figure 3. Deformation of inclusions during wire drawing [18, 19].

steel research int. 77 (2006) NO.3 159

Process Metallurgy - Steelmaking

[18, 19] , clearly indicating the good deformability of sili-
ca inclusions and bad deformability of alumina inclusions.
Hence, wire rods for tire cord are required to have spe-
cific cleanliness, such as [20]:
- Very tight chemical composition ranges (Cs ±O.O I %,
Sis±O.03%) and cleanliness requirements (S+P<0 .02%,
N<40ppm, T.O.< 15-20ppm , H s 2ppm).
- Maximum non-deformable inclusion size: 5!!m (for 0.8-
0.85 %C), lO!!m( for 0.7-0.75% C), 20!!m (for <0.7% C),
suitable inclusion morphology, and uniformly distributed
inclusions in the steel, no special inclusion accumula-
tions.
- Minimization of the central segregations forming auto-
matically during metallurgical solidification processes.
- Little surface decarburization and good surface quality.
Inclusion engineering for the tire cord steel, therefore, in-
cludes evaluation and control of the deoxidation practice
(inclusion composition , size and morphology), slag-met-
al reactions in the liquid steel fuse of synthetic top slag
and/or flux injection (inclusion composition and mor-
phology), the choice of refractory materials (inclusion
composition), and inclusion removal. The typical inclu-
sions in the tire cord steel are shown in Table 3 [21]. In-
clusions with low Al20 3content tend to be spherical [13].
The deformability of an inclusion is significantly affected
by the Al203 content as shown in Figure 4a. Inclusions
containing 20% AI203 has best deformability [13]. Howev-
er, it was also reported that for tire cord with good drawing
behavior the oxides are mainly silicates or silico-aluminates
containing 10% Ah03 [17]. The non-deformable inclusions
can be avoided by controlling the dissolved aluminium ,
[AI], in the steel. With the same Ah03 in the slag, higher
basicity of the ladle slag during LF refining produces high-
er [AI] in the molten steel. So a low basicity slag favours the
formation of deformable inclusions. When the basicity
R (=CaOfSi0 2) = 0 .8-1.5, the dissolved aluminium in the
steel should be 1-5ppm to achieve 20% Ah03 in inclusions
(Figure 4b [21)). Furthermore, the level of [AI] in the
molten steel is significantly affected by the Ah03 content in
the slag of the ladle (Figure 4c [21)). With R=1.0-1.4 , in
order to control [AI] in the range of 1-5 ppm, the slag
should contain around 8% Ah03. The similar results were
reported by Wang et al. [22, 23].
The target chemical composition of deformable inclu-
sions in the tire cord steel killed by Si/Mn is shown
in Figure 5 [13]. Preferred deoxidation inclusion by
SifMn deoxidation is spessartite (3MnO·AI203 ·3Si02 -
36.4%Si02, 20 .6%Ah0 3, 43%MnO) due to its low viscos-

Table 3. Typical inclusions in the tire cord steel [21].

Al 20.54%. s: 15.42%. 5 2.90%.

Ca 6 1.16% Al 88.54%. Fe 1.46%
sam lc of5 .5mm cord bar) sam lc of 5.5mITI cord bar)

60 20.0
c: CoO/SlOt 01 .9.......--
.g 15 10.0
::J
uc:
50 0 0
•
5.0
Ql

~ 10
40 C»
$
0
•
E 0 (1; .
30 Q Shougang China
II
Ql
<J O $ . 0 CaOISiO,=O.8
"0
c:
::l 5 20 0 0 e. • CaOlSiO,= 1.0 Ec. 1.0
'0
x
Ql
"0
10 Xl .
CD
"8
$
(J) 0 CaOISiO,=1.2

• CaO/SiO,=1.4
Kobe Steel
E:
0.5
.s 0 $ (j) CaOISiO,=1.2 ~
0
10 20 30 0 2 4 6 8 10 12 14 16 18
AI.O, Content in Inclusion (%) [AI],in the steel (ppm) 0.1
(a) (b)

AI,0 3 Content in Slag (%)

Figure 4. Relationship among the deformation of inclusions ([13]), the content of AI20 S in inclu-
(c)
sions , the dissolved aluminum in the steel , AI20 s in the slag and the bas icity of the slag [21].

160 steel research int. 77 (2006) NO.3

 Process Metallurgy - Steelmaking

ity, low wettability, excellent floating properties, and good - Use of a sub-lance in the BOF substantially lowers the
deformability. Inclusions in the bloom of the tire cord steel frequency of reblows [32].
at Kobe steel [12] and those reported by Stampa et al. [17] - Use of efficient slag stopper, such as a slag ball
are controlled right at these target regions. Zhang et al. [24] - Use of sensors to detect the slag after a little has carried
and Suito et al. [25] derived the similar chemical composi- over including infra-red [33] and electromagnetic sys-
tion of the deformable inclusions after primary deoxidation tems [34].
and during slag-metal treatment in the tire
cord steel by thermodynamic model simu-
lation on the composition of inclusions
varying with the contents of the dissolved
aluminum and oxygen in the melt, and
MnO content in the slag. An example is
shown in Figure 6 [25].

."10."
Manufacturing Processes and
Techniques of Tire Cord Steel
Manufacturing processes and techniques
to control quality of tire cord steels at sev-
eral steel plants are listed in Table 4 [12,
13, 16,21,26]. The common characteris-
tics of these processes are deoxidation with
Al-free deoxidizer, synthetic slag refining
treatment with basicity of 1-2 (mainly ~l),
careful using special flux at the tundish and
the mould and lining refractory in the ladle
and the tundish, protected pouring and
good level control and temperature control
at the mould of continuous casting, and
ElectroMagnetic Stirring (EMS) at the
mold and the second cooling zone. In this
W~ighl
section, effects of choice of deoxidizer, re-
fining methods, slag carryover from BOF
to the ladle, ladle stirring, nitrogen pickup
and mould curvature on the control of in-
clusions in tire cord steels will be dis-
cussed.

Slag Carryover from BOF to the La-

dle. An important source of reoxidation is
the carryover of slag from the steelmaking
furnace to the ladle, which contain a high
content of FeO and MnO. These liquid ox-
ides react with the dissolved elements such
as Al and Si to generate solid alumina or
silica in the liquid steel. The higher is the
FeO and MnO content in the ladle slag, the
greater is the potential for. Figure 7 shows
how T.O. in the steel correlates roughly
with the %FeO+%MnO in the ladle slag
[27-31]. Countermeasures should be taken ,-
to lower FeO and MnO contamination. At
tapping process, slag carryover can be min-
imized from steelmaking furnace to ladle by
- Increasing aim turndown carbon, avoid- 40 50 60 10
//

80
/,#'
90
,
ing reblows, thus minimizing the dis- Wright "I. AI ~ - . htlO .AI203
2
solved oxygen content in the steel, can
lower the amount of FeO in the furnace Figure 5. Target chemical composition of inclusions in the tire cord steel (deoxidation in-
slag [32]. clusions (top), and slag inclusions (bottom)) [13].

steel research into 77 (2006) No.3 161

Process Metallurgy - Steelmaking

Table 4. Manufacturing processes and techniques to produce the tire cord steel at some plants. - Designing the furnace geome-
try and tap hole location to
Steel plants Processes and techniques minimize vortex and slag car-
ThyssenKrupp Steel, Hot metal desulphurization ---+140 tonne BOF---+ SiFe deoxidation during tapping ryover [35].
Germany [21] ---+ RH (deoxidation) ---+ Vertical bending CC (260_330mm billets)
Adding a slag conditioner, a
I (Electromagnetic stirring (EMS) at the mould and the secondary cooling zone)

Saarstahl AG, Desulphurization of the hot metal treatment ---+ 165 tonne BOF---+ RH+CaSi/CaC mixture of aluminium and burnt
Germany [21] powder injection-s- CC lime or limestone, to the ladle
Unimetal, Hot Metal Dephosphorization-s-Llj-Llsfi-e-Lf (EMS)--+CC(360_320mm billets) slag to make slag reduction
France [16] Techniques: treatment can reduce FeO+MnO
· N control by use of argon in the converter, added low nitrogen graphite,
protected cast streams;
in the ladle slag to below 5%
·· EMS at the mould
Level regulation quality «±4mm level fluctuation)
[31, 32, 36, 37]. This method is
not good for the tire cord steel
·· Adapted mould powder
Adaptation of secondary cooling and setting of a constant speed all along the
production due to generating
alumina inclusions.
casting

Surnitomo Steel,
· EMS at the mould and the secondina coolins zone.
70 t BOF --+ Si or Si/Mn deoxidation during tapping-e-de-slag-»VAD argon Choice of Deoxidizer: Due to
Japan [42] bubbling and slag refining-s-bloom CC---+ EMS at the mould and the secondary
generation of the non-de-
cooling zone
Kakogawa Works, BOF (240t LD-OTB)--+ deslagging ---+ LF (Arc heating with top lance bubbling) formable inclusions in the steel
Kobe Steel, ---+ EMS in the mould and the secondary cooling zone at CC killed by Ca, Mg and AI, Si and
Japan [12, 13] Kobe Steel Techniques for harmful inclusion and segregation: [12] Mn are the best deoxidizer for

···
Controlling the chemical compositions of the inclusion
Strict control of super-heating of the molten steel
the tire cord steel, which can
EMS produce liquid spherical MnO-
POSCO, BOF --+RH --+ EMS in mould at CC (250 x 300mm billets) SiOz inclusions, easily floating
South Korea [26] Techniques: out of the molten steel. The
··Deslagging
Adding flux in the ladle furnace
equilibrium between the oxygen

···
Removing inclusions by circulating liquid steel in RH and [Si] and between the oxygen
Suppressing liquid steel reoxidation and [Mn] in the steel deoxidized
tundish with non-rice hull flux (Ah03 <0.3%)

·· proper refractories from the ladle to the SEN

Promoting floating of inclusions from ladle to mould
by Si and Mn respectively is
shown in Figure 8 [38] by
·Reducing center segregation by using EMS (Electromagnetic stirring),
lowing temperature casting, intensive cooling method at the final
which the suitable final [Si] and
[Mn] after deoxidation corre-
solidification zone, and using soft reduction in the strands)
Baosteel, Hot metal desulphurization --+300 t BOF --+RH --+Ingot casting sponding to the targeted dis-
China r2Il solved oxygen in the molten
Shougang Steel, LD top oxygen blowing --+ladle argon bubbling ---+ LF --+CaSi wire --+ steel can be obtained. Figure 8
China [21] VD degassing ---+ CC shows that if the molten steel is
only deoxidized by Si/Mn, the
1823 K dissolved oxygen in equilibrium with Si is high, inducing
[% Mnl =0.6
[%CI=0.8 pinholes under the surface of the blooms. Further deoxida-
[% Si] = 0.3
tion has to be done during LF by the synthetic slag refining.
a) iso-jppm All The main deoxidation product by SilMn is 3MnO-Ah03-
3SiOz (37% sio., 20% Ah03, 43% MnO), which is de-

40

35

MoO
i,e; 30

a; 25
-!l
.s 20 0
o 0
...: 15
0
0
b) iso-[ppm 0] 10 0

0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0

MoO
FeO+MnO in ladle slag (%)

Figure 6. Iso-[ppm AI] (a) and iso-[ppm 0] (b) lines in MnO-Si0 2- Figure 7. Relationship between FeO+MnO in ladle slag and T.O. in
AI203 system for the tire cord steel [25]. steel after RH-OB treatment [27, 28] and argon bubbllnq [30].

162 steel research int. 77 (2006) NO.3

 Process Metallurgy - Steelmaking

formable, with low viscosity and low melting • Matoba et al. (1843K) • Suzuki et al. (18Z3K)
• Maloba et al: (1898K) II Suzuki et al. (1873K)
temperature and rises well in the molten steel. n Suzuki et al. (l923K)
o Matoba et al. (1953K)
If Ah03 is> 20% in the inclusion, Ah03 will .. Gokcen and Chipman (1873K) + Segawa et al. (1873K)
precipitate, and if Alz03 <20%, SiO z will pre- A Tszen-Tszi et al. (1873K) x Shevtsov et al. (1873K)
cipitate. Both the precipitated pure Ah03 and o Hilty and Crafts (1873K) present work
SiO z are non-deformable. During rolling , the
precipitated SiOz, Alz03 just break from the
deformable matrix of inclusions. During -1 molten Fe
cooling, the concentration of dissolved oxy-
gen/nitrogen/sulphur in the liquid becomes
5"
';!?,
0
larger while the solubility of those elements en
en
decreases , therefore inclusions precipitate. ""
E
........
Pure silica phase also precipitates from the 0.0 -2
matrix of inclusions during cooling and solid- .9
ification process of the steel, as shown in
Table 5 [39]. The size of these precipitates in-
creases with decreasing cooling speed. Thus
fast cooling favours the precipitation of small -2 -1 o
pure silica phases from the matrix of the in-
clusions. It was also reported that in Mn-Si
:::mm
~
l 923K
killed steels, alumina content in MnO-SiO z- I~ Fot O-Mn O FOtO-MnO / 1873K

iii )
1- (!Iquldslag) (solid solu tl on)= ( (" l 823 K
Ah03 inclusions is affected greatly by the X Janke It . 1.
temperature from 1848 to 1773 K during + OomRoroy ot 01.

10" I~923~Klljif~1111
cooling process [40]. o
~
til
Steel Refining Operations. There are sev- til I-
Cll
eral steel refining methods are used to pro- §.
duce tire cord steels, such as ladle arc refining
process [13, 41], vacuum treatment such as
VAD [42], RH treatment [13,26], ladle syn-
thetic slag refining by Ladle Furnace
(LF)[13], and VD process [21], as listed in
Table 4. It should noticed that some steel
plant proceed the steel deoxidation during
tapping process [42]. In spite of what steel re- Figure 8. Equilibrium between the oxygen and Si, Mn in the molten steel when the
fining method is used, there is an important steel is deoxidized bySi, Mn respectively [38].
step before steel refining--de-slag process,
reported by many steel plants [13,26,41,42].
Vacuum refining may increase the dissolved aluminum
and magnesium in the molten steel by reducing refractories
and slag. The practice at Kakogawa Works of Kobe Steel in-
dicates that LF refining produces lower wire breakage than
RH vacuum degassing [13]. Kawasaki Steel compared three
steel refining routes to produce tire cord steels: 1) RH, 2)
RH+slag refining, and 3) Ar bubbling+ Slag refining. Route
I is the worst, with [AI] = 5-10 ppm in the molten steel, and
route 3 is the best, with [AI] < 3 ppm and T.O. = 35 ppm in
the steel. Though adding Ca wire or CaSi powder into the
steel can modify the shape and defonnability of inclusions
[43,44], this method is rare to be used to produce tire cord
steels. Ca is very reactive , and it is only effective after the
steel has been deoxidized and if slag entrainment, especial-
ly with FeO and MnO, can be avoided . Adding Ca into the
steel easily generates high CaO inclusions, which signifi-
cantly worsens the quality of tire cord steels.
As an example the oxide activity before and after syn-
thetic slag treatment is shown in Figure 9 [45]. Functions
of the slag on the top of the ladle during steel refining in-
clude desulphurization, deep deoxidation, insulating, ab-
sorbing inclusions, and preventing reoxidation by air. Thus ,
o
1873K tl
1823 K
o
lvIonehov otol.
ED fl F1tlschtr ot 01.
.... Chlpmln I t II.
<l 0 C> Korber ot II.
I- ~ • ~ Hilly 01 II .
-+ +++++11\ f::, 0 'V Tluhosh l&Hlno
11111 I
H- I
I
[mass%Mn]
10° 10' 10'
slags during the steel refining of the tire cord steel should
have the following characteristics :
- Low oxygen potential (low FeO and MnO),
- Low melting temperature , good fluid ability favouring the
reaction between the molten steel and the slag ,
- Ability to absorb inclusions and modify the morphology
of inclusions ,
- No new phase precipitation due to the absorption of de-
oxidation products during refining,
- Suitable basicity to desulphurization and deoxidation ,
- Suitable MgO to avoid lining erosion.
The basicity, Alz0 3 content , viscosity and melting tempera-
ture of slags affect the final composition of inclusions. It
was reported that in slags with basicity of 0.8-1.2 it is easi-
er to control <10% Alz0 3 in the slag. High basicity slags fa-
vor deoxidation [46] but generate non-deformable inclu-
sions. The typical composition of slags used in the tire cord
steel production at several works are listed in Table 6 [21].
Kobe steel extensively investigated the effect of the slag
composition on the amount of inclusions in the tire cord
steel. As shown in Figure 10 [13], 70% CaO-30% CaF z and
67%CaO-23AhOrlO%CaFz systems produce the best re-

steel research int. 77 (2006) No.3 163

Process Metallurgy - Steelmaking

suits. lemura et al. [42] tried four kind of slags: A:48% amounts of magnesium, calcium and aluminum dissolved in
CaO-32% Ah03-20% CaF 2; B: 65% CaO-18% Ah03-15% the liquid steel are lowered. At Kakogawa Works (Kobe
CaF2 ; C: 85% CaO-15% CaF2 ; D: 46% CaO-2% Ah03- Steel) with the synthetic slag treatment during ladle arc re-
47% Si02-5 % CaF2. System D has a small number of non- fining , the inclusions are modified into the target region of
deformable inclusions with low melting point, and this slag the deformable inclusions [13].
has been finally used at Sumitomo. At Sumitomo Steel, by Ladle stirring and refining processes greatly promote in-
using the synthetic slag treatment (46%CaO-2%AI203- clusion growth and removal. Some metallurgical reactions
47%Si025%CaF2), non-Al-O, high Zr0 2 ladle lining re- require strong mixing of metal and slag (e.g. desulphurisa-
fractory and high MgO tundish refractory lining, the ToO. is tion and dephosphorisation), whereas others require gentle
controlled below 22ppm and Ah03 is 1ppm in the tire cord mixing at the metal/slag interface and maintenance of an
steel. At NYCO Minerals [41], the steel is firstly deoxidized unbroken slag layer (e.g. deoxidation and inclusion re-
by SilMn, generating 3MnO'AI203'Si02 inclusions ("Spe s- moval). Different processes produce different stirring pow-
saryite") , then Wollastonite (CaO'Si0 2) is added to start la- ers. The effect of stirring power on the rate of oxygen re-
dle Arc refining. The spessaritite inclusions are transformed moval is shown in Figure 11 [4,47], which reveals that an
into CaO'Ah03'2Si02 inclusions ("Anorthite"), and the increasing stirring rate helps to remove inclusions, unless it
becomes excessive. Suffi-
cient stirring time (> 10 min)
Table 5. Inside morphology and inside composition of large inclusions from deoxidation or reoxida- [48] after alloy addition is
tion in the steel deoxidized by SilMn [39].
also important to allow the
alumina inclusions to circu-
2 2 3 4
late up to the slag and be re-
0.13 0.03
moved. Extremely vigorous
0.07
stirring or excessive treat-
3.68 3.70 0.76 0.82
ment time are bad for several
39.28 40.12 93.92 95.48
reasons. For a faster upward
1.65 1.51 0.34 0.30
circulation of the steel onto
0.01 O.oJ
0.07 0.30
the slag layer may expose a
0.05
1.44 1.48 0.38 0.03
slag-free region of the steel
0.43 0.52 0.05 0.04
surface to absorb air [30, 49] ,
48.42 48.99 4.23 2.47 perhaps induce slag entrain-
1.04 1.18 0.06 0.03 ment, and ladle lining erosion
may also become a problem .
It is suggested to first stir
3 2 3 4 vigorously to encourage mix-
0.2 ing and the collision of small
0.16 0.15 inclusions into large ones,
3.90 4.21 0.60 0.60 followed by a "final stir" that
38.78 38.19 95.95 97.24
slowly recirculates the steel
to facilitate their removal
0. 14 2.29 0.07
into the slag while minimiz-
2.13 0.0 1 0.2 1 0.00
ing the generation of more
0.09 0.17 0.04 large inclusions via collisions
2.40 2.34 0.36 0.30 [50,51].
0.21 0.37 0.05 0.05
47.43 47.78 2.42 1.31 Control of Nitrogen Pick-
0.8 1 0.59 0.04 0.04
up. The difference in nitro-
gen content between steel-
0.0 1
making vessels is an indica-
tor of the air entrained during
Table 6. Typical slag composit ion (wt.%) for the slag treatment to produce the tire cord steel [21]. transfer operations . Note that
oxygen pickup is always
CaO Si0 2 AhO, MgO CaF 2 R [0] Al powder many times greater than the
Sanyo. Japan 57.8 13.8 15.8 4.3 7.8 4.5 5.8 measured nitrogen pickup ,
SKF , Sweden 50-55 10 30 5 0 5.0 8.1 due to its faster absorption
A plant in China 45 23 12 20 0 2.0 10 kinetics at the air steel inter-
Jiugang, China 50-55 25- 30 15-20 5 face [52]. In addition , nitro-
45 10
gen pickup is faster when the
Kawas aki 45
oxygen and sulfur contents
Sumitomo 46 47 2
are low [53,54]. To reduce
NYCO [41] 47.5 51
nitrogen pickup, deoxidation

164 steel research int. 77 (2006) NO.3

 Process Metallurgy - Steelmaking

Before After d[O)/dl= • Ko (0)

Treatment Treatment (0): ppm

j
.5
----------
OslO,
IJoInO
aA',o,
0
/I
0
•
...
•
tmin
Ko: min"1

~< 1. 0 _- .... CIslO.

~ ,. 0 "
j o
.
c:s
o
iii
c:s III
III III t:.
III Ar gas bubbling
0 ASEA-SKF(I)

III •
[J
ASEA-SKF(II)
voe (NK-PERM)
III von (Convent.)
V RH (NK-PERM)
... RH (Convent.)

1 2 3
10 10 10
0.1 1.0
Equilibrium Value of /Jato.. IJoIno, Stirring power (Watt/ton)
a......" with MoltenSteel
Figure 9. Oxide activity before and after synthetic slag treatment Figure 11. Effect of stirring power on deoxidation rate in various re-
[45]. fining processes: Ar gas bubbling [4]; ASEA-SKF [4]; VOO and RH
[47].

is best carried out after tapping. Nitrogen E 80",.-----------------.

c-
pick-up can be controlled at 1-3 ppm from o. 70
ladle to mold for the Al-killed steel [32,52, "':::: 60
54-67]. Using an optimized shrouding sys- 5~ 50
'iii 0
tem greatly lowers reoxidation during trans- .=! ;, 40
to) e
fer operations [30, 59, 63, 68-71]. It is very oS.- 30
_'0
important to carefully seal the joints in the o c:: 20
~&.
shrouds, both to improve cleanliness and to § K: 10 AlzQJ
prevent clogging [55]. Inert gas can pro- ° t O .................- ......-....--.l.-.......-~H=~~'"'::-~
tect the steel from air reoxidation in many ~.§. withOut flux CoO-CoFz CoO-SiOz
70 30 50 50
ways [54, 72, 73]. Injecting argon into the
tundish stopper rod and improved sealing
decreased nitrogen pickup from tundish to
slab [62,74,75].

Thndish Operations. The continuous

casting tundish serves as a buffer and links
the discontinuous process of the secondary J
metallurgy in the ladle with the continuous
casting process in the mold. Modem steel- ~L-ZI:- After ladle arc
making tundish is designed to provide max- refining
imum opportunity for carrying out various
metallurgical operations such as inclusion
separation, alloying, inclusion modification
by calcium treatment, superheat control,
thermal and particulate homogenization,
leading to the development of a separate
area of secondary refining of steel, referred
to as "Tundish Metallurgy".
Techniques have been developed to im-
prove inclusion removal and prevent steel
reoxidation, such as suitable tundish pow-
ders and lining refractories and flow control
devices. Many studies reported that the syn-
thetic slag treatment during LF refining and Figure 10. Effect of the synthetic slag treatment on the inclusion amount and inclusion
using suitable lining refractory in ladle and composition in the tire cord steel [13].

steel research int. 77 (2006) NO.3 165

Process Metallurgy - Steelmaking

Table 7. Special refractory used during the production of tire cord steels at pasco [26]. - Forced coagulation in suitable
turbulent zones and floating of
Non-tire cord steel Tire cord steel
inclusions at other zones, aas-
Collector nozzle 75%AI,O" 19% SiO" 5%C 80%AI,O" 15% SiO" 5%C
similated by cover slag,
SEN 36%AI,O" 23% SiO" 28%C 65MgO,18C - Avoiding "open (red) eye", i.e.
Tundish stopper 46%AI,O" 18% SiO" 25%C 65MgO,18C uncovered surface of molten
steel to prevent air absorption.
Removal of inclusions can be
optimized by the use of flow con-
10 4 r-- - - - - - - - - - - - - ---., trol devices, which has also been accomplished at
Shougang Steel [15].

Caster Curvature. Curved mould machines are known

37 11m ~ Nonmetallicinclusionsize
10 0
Loose side Center Fixed side
Figure 12. Distribution of inclusions extracted by Slime method
from the bloom samples with the same steel grade [79]
(300mmx500mm bloom, 13°C super heat. 1CC: curved mould, 18-
tonne tundish, casting speed 0.5m/min; 2CC: vertical bending cast-
er (2.5m), 40 tonne tundish, casting speed 1m/min.)
Figure 13. Effect of carbon and interlamellar spacing in pearlite
[20].
to entrap more particles than straight (vertical) mold cast-
ers,[75, 76] because the particles gradually move upwards
towards the inside radius while they spiral with the liquid in
the lower recirculation zone [77-79], as shown in Figure 12
[79]. Most particles are captured 1-3 m below the menis-
cus, independent of casting speed [77, 80], which corre-
sponds to a specific distance through the strand thickness
[81]. Often, inclusions concentrate at the surface and at one-
eighth to one-quarter of the thickness from the top of the in-
side radius surface [29, 82-84]. The vertical bending caster
has fewer inclusions and pinholes, which are distributed
deeper, relative to the curved caster [75, 79].
Techniques to Lower Center Segregation of Elements
(S, C, P) and Center Porosity. It was observed that segre-
gation of carbon in the core of wire rod bursts during draw-
ing, as shown in Figure 13 [20]. The heavy segregation
leads to internal cracking as early as at the wiredrawing
stage, and this internal cracks causes wire breaks in the
course of further cold working. This entails high costs if the
wire breaks at the final stage of the processing. The center
segregation can be reduced by decreasing the superheat,
lowering the casting speed, using ElectroMagnetic Stirring
(EMS), intensive cooling method at the final solidification
zone, and on-line soft reduction [12, 26]. Detailed tech-
niques employed at several steel plants are listed in Table 4.
Figure 14 clearly shows the positive effect of EMS on de-
creasing the segregation in the tire cord steel [79]. The
length of dendrites at the solidification front in the continu-
ous billets with EMS is far smaller than that without EMS,
as shown in Figure 15 [85].

tundish are the most efficient approach to control inclusions
in the tire cord steel. High Alz03 lining refractories at ladle
and tundish should not be used in the production of tire
cord steels [42]. POSCO uses special low Al203 tundish
flux (Si02 54.36%, CaO 43.31%, MgO 0.25, Al203 0.27)
and special lining refractories (Table 7 [26]) to decrease the
number of undeformable inclusions (alumina/aluminate)
and improve steel cleanliness by suppressing liquid steel re-
oxidation [26]. Each tundish is designed in a way as to re-
alize an optimal flow and therefore better cleanliness of the
steel by providing:
- High average residence time,
- Small severe turbulence, dead and short-circuit volumes,
- Large volume of laminar flow region,
Summary
The control of inclusions in tire cord steels and tech-
niques used in the production process are extensively re-
viewed. Inclusion and segregation requirements for the tire
cord steel are discussed. The deformability of an inclusion
is significantly affected by its Alz03 content. Inclusions
containing 20% Alz03 has best deformability. The non-de-
formable inclusions can be avoided by controlling the dis-
solved aluminium in the steel. Low basicity slags favour the
formation of deformable inclusions. When the basicity
R(=CaO/Si0 2)=O·8-1.5, the dissolved aluminium in the
steel should be l-5ppm to achieve 20% Alz03 in inclusions.
With R=1.0-1.4, in order to control [AIls in the range of 1-
5ppm, the slag should contain approximately 8% Alz03. In-

166 steel research int. 77 (2006) NO.3


(a) Without EMS and the application of a suitable taper of the roll
gaps to compense for solidification shrinkage (super heat=23°C,
casting speed=O.9m/min)
(b) With EMS and the application of a suitable taper of the roll gaps
to compense for solidification shrinkage (super heat=23°C, casting
speed=1.1m/min)
Figure 14. Solidification Structure of Steel (0.47C) at Kimitsu
Works, Nippon Steel [79).
elusion engineering for the tire cord steel includes control
of deoxidation practice , slag-metal reactions, use of syn-
thetic top slag, choice of refractory materials, and inclusion
removal. In the production of the tire cord steel, the follow-
ing process are often used: deoxidation with Al-free deoxi-
dizer, synthetic slag refining treatment with basicity of 1-2
(mainly -I) by LF process, protected pouring and good lev-
el and temperature control at the mould, carefully using
special flux and refractories at ladle, tundish and mould,
and ElectroMagnetic Stirring (EMS) in the mould and the
secondary cooling zone.
(A20055073; received on 9 January 2005,
in final form on 19 May 2005)
Contact:
Prof. Dr. Lifeng Zhang, Department of Materials Science
and Engineering, Norwegian University of Science and
Technology, Alfred Get: vei 2,7491 Trondheim/Norway
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The Influence of Non-Metallic Inclusions Physical State on Effectiveness of the

Steel Filtration Process
Krystian Janiszewski, Zdzislaw Kudlihski

Silesian University of Technology, Department of Metallurgy, Katowice, Poland

The work presents theoretical fundamentals of the process of refining molten steel from liquid non-metallic inclusions, using the method of
filtration with ceramic filters - the thermodynamic precondition for the absorption of liquid non-metallic inclusions on the surface of a ceram-
ic filter. The theoretical consideration has been supported by the results of laboratory tests on the filtration of steel which was previously re-
duced with complex deoxidants giving liquid products of deoxidization. The filtration process of steel melts reduced with complex deoxidants
of type AI-Mn-Si has proved to be more efficient. The deoxidation products were identified on the filtration surface of the ceramic filters.

Keywords: steel, refining, ceramic filter, non-metallic inclusions.

Introduction lower in value than one, in opposition to the individual ox-

The oxidative nature of the steelmaking processes is a
predominant cause of heavy oxygenation in the metal bath
at the final stage of steelmaking. This is why deoxidation is
considered an obligatory technique in the process of mak-
ing killed steel. Sedimentary deoxidation is the most popu-
lar method of steel deoxidation. Besides its numerous un-
questioned advantages there is a disadvantage of the
method, essential for steel cleanness, which should be tak-
en into account: the possibility of polluting the steel with
the generated non-metallic phase, being the product of de-
oxidizing chemical reactions [1]. The chemical composition
and the physical state of the deoxidation products of the
sedimentary method in the form of non-metallic inclusions
(NMI) are in close relationship with the deoxidation
method, especially with the quantity and kind of the deoxi-
dizers used. Steel deoxidation with complex deoxidizers
generates multiphase liquid products. In case of deoxidation
with aluminium, ferrosilicon and ferromanganese, efforts
should be made to generate deoxidation products of com-
position according to 2Alz03'5Si02'2MnO, which tum into
liquid as soon as the temperature reaches 1200°C (1473 K).
Deoxidation with complex deoxidizers is a more effective
process compared to single ones. This is due to the fact that
in the "complex" nucleus the individual components mutu-
ally dissolve each other and their activity parameters are
ides (generated in the deoxidation process with a single de-
oxidizer) which have activity parameters equal to one [2].
A theory explicated thirty years ago on refining molten
steel of NMI with a filtration method using ceramic filters
was directed to solid inclusions generated in steel deoxi-
dized with aluminium [3,4,5,6,7]. Results of these investi-
gations point to a future feasibility of the introduction of
steel filtration as a regular component of steelmaking
processes [8,9]. Steel filtration of liquid non-metallic in-
clusions - the products of sedimentary deoxidation with the
aid of complex deoxidizers - has generally been neglected
in the researches mentioned. Only in few papers [e.g. 10
and 11] the physical condition of NMI was noted as a fac-
tor influencing the steel filtration process performed with
the aid of ceramic filters. This is why the aim of this re-
search work is to describe the theoretical fundamentals for
steel filtration of liquid NMI performed with the aid of mul-
ti-hole ceramic filters, and to identify the influence of the
steel deoxidation method (with a single or complex deoxi-
dizer) on the filtration process effectiveness.
Thermodynamical Conditions for Liquid
NMI Adsorption by Ceramic Filters
A spontaneous run of the process of liquid NMI adsorp-
tion by the ceramic filter surface has to be associated with a

steel research int. 77 (2006) No. 3 169